Olefin metatheses in metal coordination spheres: Versatile new strategies for the construction of novel monohapto or polyhapto cyclic, macrocyclic, polymacrocyclic, and bridging ligands

Article abstract of DOI:10.1002/1521-3765(20010917)7:18<3931::AID-CHEM3931>3.0.CO;2-Y

The broad applicability of the title reaction is established through studies of neutral and charged, coordinatively saturated and unsaturated, octahedral and square planar rhenium, platinum, rhodium, and tungsten complexes with cyclopentadienyl, phosphine

Full text of DOI:10.1002/1521-3765(20010917)7:18<3931::AID-CHEM3931>3.0.CO;2-Y

FULL PAPER
Olefin Metatheses in Metal Coordination Spheres: Versatile New Strategies
for the Construction of Novel Monohapto or Polyhapto Cyclic, Macrocyclic,
Polymacrocyclic, and Bridging Ligands
Johannes Ruwwe,[a, b] Jose Miguel Martín-Alvarez,[b] Clemens R. Horn,[a] Eike B. Bauer,[a]
Slawomir Szafert,[a, c] Tadeusz Lis,[c] Frank Hampel,[a] Phillip C. Cagle,[b] and
John A. Gladysz*[a]
ˆ
Abstract: The broad applicability of the
title reaction is established through
studies of neutral and charged, coordi-
natively saturated and unsaturated, oc-
tahedral and square planar rhenium,
platinum, rhodium, and tungsten com-
plexes with cyclopentadienyl, phos-
phine, and thioether ligands which con-
tain terminal olefins. Grubbsꢀ catalyst,
PPh), formation of five-membered het-
erocycles (96 ± 64%; crystal structure
product); cis-[(Cl)2Pt(S(R)(CH2)6CH
CH2)2], intra-/intermolecular macrocyc-
lization (R ˆ Et, 55%/24%; tBu, 72%/
< 4%); trans-[(Cl)(L)M(PPh2(CH2)6-
E ˆ PMe);
[(h5-C5Me5)Re(NO)(PPh-
n‡
ˆ
((CH2)6CH CH2)2)(L)] nBF4 (L/n ˆ
CO/1, Cl/0), intramolecular macrocycli-
zation (94 ± 89%; crystal structure L ˆ
ˆ
CH CH2)2] (M/L ˆ Rh/CO, Pt/C6F5) in-
tramolecular macrocyclization (90 ±
83%; crystal structure of hydrogenation
product, M ˆ Pt); fac-[W(CO)3(PPh-
ˆ
Cl);
fac-[(CO)3Re(Br)(PPh2(CH2)6-
ˆ
CH CH2)2]
and
cis-[(Cl)2Pt(PPh2-
ˆ
(CH2)6CH CH2)2], intramolecular mac-
rocyclizations (80 ± 71%; crystal struc-
tures of each and a hydrogenation
((CH2)6CH CH2)2)3],
intramolecular
ˆ
[Ru( CHPh)(PCy3)2(Cl)2], is used at 2 ±
trimacrocyclization (83%) to a complex
mixture of triphosphine, diphosphine/
monophosphine, and tris(monophos-
phine) complexes, from which two iso-
mers of the first type are crystallized.
The macrocycle conformations, and ba-
sis for the high yields, are analyzed.
9 mol% levels (0.0095 ± 0.00042m, CH2-
Cl2). Key data are as follows: [(h5-
ˆ
C5H4(CH2)6CH CH2)Re(NO)(PPh3)-
Keywords: Grubbsꢀ catalyst ´ mac-
rocycles ´ metathesis ´ trans-span-
ning ligands
(CH3)],
(95%);
intermolecular
metathesis
[(h5-C5H5)Re(NO)(PPh3)(E-
(CH2CH CH2)2)] TfO (E ˆ S, PMe,
‡
ˆ
group active in this area, although turnover numbers with
their tungsten/silane catalyst system were low (<4). Then
followed applications in ADMET[3a] and ring-opening[3b,c]
polymerizations of unsaturated ferrocenophanes (Scheme 1B).
Sauvage subsequently described an elegant series of catenane
syntheses (Scheme 1C).[4, 5] These processes, effected with
modern alkylidene catalyst precursors, featured high yields
and turnover numbers.
These auspicious beginnings nevertheless posed more
questions than answers. For example, do coordinatively
unsaturated substrates react as effectively as the eighteen-
valence-electron educts in Scheme 1? Are a broad spectrum
of ligands, and a range of formal charges, tolerated? Can non-
catenated macrocycles be accessed in high yields? If all of
these answers were to be yes, olefin metathesis would have
immense utility in inorganic and organometallic synthesis. We
could envision a number of specific applications to problems
under investigation in our laboratory.
Introduction
The olefin metathesis reaction is making a profound impact
upon every branch of organic synthesis, and novel new
applications are being developed at an astonishing pace.[1]
However, there have been far fewer efforts in inorganic or
organometallic synthesisÐin other words, olefin metatheses
in metal coordination spheres.[2±7] Scheme 1 illustrates repre-
sentative examples. The first is one of several reported by
Rudler and co-workers (Scheme 1A).[2] They were the earliest
[a] Prof. Dr. J. A. Gladysz, Dr. J. Ruwwe, Dipl.-Chem. C. R. Horn,
Dipl.-Chem. E. B. Bauer, S. Szafert, Dr. F. Hampel
Institut für Organische Chemie
Friedrich-Alexander Universität Erlangen-Nürnberg
Henkestrasse 42, 91054 Erlangen (Germany)
Fax : (‡49)9131-85-26865
[b] Dr. J. Ruwwe, J. M. Martín-Alvarez, P. C. Cagle
Department of Chemistry, University of Utah
Salt Lake City, Utah 84112 (USA)
Towards these ends, we designed the series of test reactions
in Scheme 2. In general, we sought to probe whether
intermolecular reactions could be effected with simple
[c] S. Szafert, T. Lis
Department of Chemistry, University of Wroclaw
F. Joliot-Curie 14, 50-383 Wroclaw (Poland)
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J. Gladysz et al.
FULL PAPER
Scheme 2. Conceptual planning: selected categories of olefin metathesis
reactions.
selected data have been communicated.[6] This full paper
provides a complete account of these and many previously
unreported data, integrating and interpreting all results in the
context of Scheme 2 and the metal/ligand compatibility
questions posed above. While our work was in progress, new
contributions appeared from other laboratories.[7] These are
presented and analyzed in the Discussion section.
Scheme 1. Some previous examples of olefin metathesis in metal coordi-
ˆ
nation spheres. a) WOCl4/Ph2SiH2; b) [W( CH-o-C6H4OMe)(ORf)2-
ˆ
ˆ
( NPh)(THF)]; c) [Ru( CHPh)(PCy3)2(Cl)2] (1).
monoolefinic substrates as in Scheme 2A, the competition
between ring closing metathesis and intermolecular reactions
with the various diolefinic substrates in Scheme 2B ± D,
dependencies on substrate stereochemistry, such as with the
cis/trans isomers in Scheme 2C ± D, and selectivity issues of
the type posed in Scheme 2E.
Results
Intermolecular reactions: For many of the metatheses in
Scheme 2, we anticipated competition between intermolecu-
lar and intramolecular pathways. We thus began with a
monoolefinic test substrate that could only give an intermo-
lecular reaction (Scheme 2A). As shown in Scheme 3, the
racemic chiral rhenium methyl complex [(h5-C5H5)Re-
(NO)(PPh3)(CH3)] (2)[9] was treated with nBuLi to generate
ˆ
We selected Grubbsꢀ catalyst, [Ru( CHPh)(PCy3)2(Cl)2]
(1),[8] which was known to exhibit good functional group
tolerance, when we began reaction screening in 1998. We
enjoyed a very high rate of success from the outset, and
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Olefin Metathesis
3931±3950
Z/E mixtures and lower the probability of intermolecular
reaction. As shown in Scheme 4, a CH2Cl2 solution of the known
cationic rhenium di(allyl) thioether complex [(h5-C5H5)Re-
‡
(NO)(PPh3)(S(CH2CH CH2)2)] TfO (8, 0.0021m)[15] was
ˆ
treated with 1 (2 mol%) at reflux. After 3 h, NMR spectra of
the homogeneous mixture showed an essentially quantitative
reaction. Workup gave the dihydrothiophene complex [(h5-
‡
ˆ
C5H5)Re(NO)(PPh3)(SCH2CH CHCH2)] TfO (9) in 75%
yield. Interestingly, ring closing metatheses of free di(allyl)
thioether with catalysts similar to 1 fail or proceed in very low
yield,[16] presumably due to strong sulfur binding to the
alkylidene carbon or metal. Thioether ligands are easily
detached from the rhenium Lewis acid in 8 and 9.[15] Hence,
the rhenium can serve as a protecting group for the metathesis
of olefinic thioethers.
The cationic rhenium di(allyl) phosphine complexes [(h5-
‡
ˆ
C5H5)Re(NO)(PPh3)(PR(CH2CH CH2)2)]
TfO
(10,
Scheme 4; R ˆ a, Me; b, Ph) were synthesized by reac-
tions of the free phosphines and the triflate complex [(h5-
C5H5)Re(NO)(PPh3)(OTf)], as reported for similar species
Scheme 3. An intermolecular metathesis reaction. a) nBuLi, THF,
ˆ
308C; b) Br(CH2)6CH CH2 (4); c) H2 (1 atm), cat. [Rh(PPh3)3(Cl)],
toluene.
the known lithiocyclopentadienyl complex [(h5-C5H4Li)Re-
(NO)(PPh3)(CH3)] (3).[10] Then the commercially available
ˆ
a,w-bromoolefin Br(CH2)6CH CH2 (4) was added. Workup
gave the alkylcyclopentadienyl complex [(h5-C5H4(CH2)6-
ˆ
CH CH2)Re(NO)(PPh3)(CH3)] (5) in 54% yield. Metathesis
substrates were characterized by IR and NMR (1H, 13C, 31P)
spectroscopy, and gave correct microanalyses (Experimental
Section). However, since close relatives lacking olefins have
been characterized (e.g., the methylcyclopentadienyl ana-
logue of 5),[10] the spectroscopic data are not discussed.
A CH2Cl2 solution of 5 (0.0095m) was treated with Grubbsꢀ
catalyst 1 (3 mol%). After 1.5 h at reflux, workup gave the
metathesized dirhenium complex 6 shown in Scheme 3 in
95% yield as a 23:77 mixture of Z/E isomers. Stereochemistry
was assigned on the basis of previously established 13C NMR
Scheme 4. Metatheses within a ligand: small ring syntheses.
shielding trends.[11] Isomer ratios were measured by 1H or 31
P
NMR spectroscopy.[12] Metathesis products were character-
ized analogously to 5, and unless noted gave correct micro-
analyses. However, no special attempts were made to separate
Z/E isomers. We sought instead to effect hydrogenations, a
process with good precedent in metal coordination spheres,[13]
including Sauvageꢀs catenanes.[4, 5]
Accordingly, 6 and H2 (1 atm) were reacted in toluene in
the presence of Wilkinsonꢀs catalyst. Workup gave the
corresponding saturated dirhenium complex 7 shown in
Scheme 3 in 93% yield. Complex 7 was characterized
analogously to 5 and 6. Although it would be expected to be
a mixture of meso/rac configurational diastereomers, NMR
spectra showed only a single set of signals. Other diastereo-
meric dirhenium complexes with comparable metal ± metal
distances behave similarly.[14]
earlier.[17] A CH2Cl2 solution of 10a (0.0017m) was treated
with four portions of solid 1 (8 mol% total) over the
course of 1 h at room temperature. Workup afforded the
2,5-dihydrophosphole complex [(h5-C5H5)Re(NO)(PPh3)-
‡
ˆ
(P(Me)CH2CH CHCH2)] TfO (11a) in 96% yield. A
similar reaction of 10b (0.00087m CH2Cl2, 4 mol% 1) gave
spectroscopically pure 11b in 64% yield.[18] Other phosphorus
heterocycles have been prepared by olefin metathesis,[19] but
only in one study from unprotected phosphines. The crystal
structure of 11a was determined as described in the Exper-
imental Section, and the structure of the cation is shown in
Figure 1.
Metatheses with the potential to give macrocycles were
examined next. Two new phosphine ligands were first
[20a]
prepared. As shown in Equation (i), the reaction of LiPPh2
or commercial KPPh2 and the commercial olefinic bromide 4
ˆ
Intramolecular reactions: Cyclization within one ligand. Meta-
theses of the type in Scheme 2B were examined next. Sub-
strates that would give small rings were selected first, to avoid
gave the phosphine monoolefin PPh2(CH2)6CH CH2 (12) as a
viscous colorless liquid in 88% yield after workup. The
ˆ
phosphine diolefin PPh((CH2)6CH CH2)2 (13) was obtained
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J. Gladysz et al.
FULL PAPER
Scheme 5. Metatheses within a ligand: macrocycle syntheses. a) LiAlH4/
THF; b) aq. HCl/CH2Cl2; c) H2 (4 atm), cat. [Rh(PPh3)3(Cl)], toluene/
ethanol.
5
ˆ
chloride complex [(h -C5Me5)Re(NO)(PPh((CH2)6CH
CH2)2)(Cl)] (15) in 56% yield.
Next, CH2Cl2 solutions of 14 and 15 (0.00125 ± 0.00070m)
were treated with 1 (4 ± 5 mol%) at room temperature
(Scheme 5). After 12 ± 14 h, workups gave the fifteen-mem-
Figure 1. Structures of rhenium cyclic and macrocyclic monophoshine
complexes 11a ´ (CH2Cl2) (top, cation only), (Z)-17 (middle), and (E)-17
(bottom). Key bond lengths [Š] and angles [8], 11a: Re P1 2.3768(11),
Re P2 2.3594(11), Re N1 1.764(3), P1-Re-P2 97.20(4), P1-Re-N1 91.18(9),
P2-Re-N1 92.26(9); (Z)-17 and (E)-17: Re P 2.3836(14), Re N 1.785(5),
Re Cl 2.429(2), P-Re-N 90.56(14), P-Re-Cl 87.71(5), N-Re-Cl 98.91(13).
bered macrocyclic phosphine complexes [(h5-C5Me5)Re(NO)-
‡
(P(Ph)(CH2)6CH CH(CH2)6)(CO)] BF4 (16) and [(h5-
ˆ
ˆ
C5Me5)Re(NO)(P(Ph)(CH2)6CH CH(CH2)6)(Cl)] (17) in
94 ± 89% yields. The former was a 44:56 mixture of C C
ˆ
in 78% yield from Li2PPh[20b] and 4 [2.0 equiv; Equa-
tion (ii)].[21] Both can be stored indefinitely under inert
atmospheres, but are air sensitive (13 > 12).
isomers, and the latter a 42:58 mixture, as assayed by 1H NMR
spectroscopy.[4b, 23] Hence, macrocyclization is spectacularly
successful, both with cationic and neutral substrates, and in
the absence of templating functionality that seems to be
necessary for many ring closing metatheses of purely organic
substrates.[11, 24]
Br(CH2)6CH CH2 + MNu
Nu(CH2)6CH CH2 + MBr
4
Nu = 12, PPh2
27, SEt
(i)
28, StBu
Complex 17 could also be prepared from 16, using the same
LiAlH4/HCl sequence used for the conversion of 14 to 15.[25]
Reaction of 17 and H2 (ca. 5 atm) in the presence of
Wilkinsonꢀs catalyst gave the corresponding saturated macro-
cycle [(h5-C5Me5)Re(NO)(P(Ph)(CH2)14)(Cl)] (18) in 72%
yield (Scheme 5). Of the preceding compounds, the most
easily crystallized proved to be olefin 17. The structure was
determined as described in the Experimental Section. Refine-
ment showed a 58:42 mixture of Z/E isomers in the lattice,[23]
with identical atomic coordinates for all atoms except the
macrocycle carbons. Both structures are given in Figure 1, and
analyzed below.
PPh((CH2)6CH CH2)2 + 2 LiBr
2 Br(CH2)6CH CH2 + Li2PPh
(ii)
4
13
The acetonitrile ligand in the pentamethylcyclopentadienyl
‡
complex [(h5-C5Me5)Re(NO)(NCCH3)(CO)] BF4 is dis-
placed by numerous phosphines.[22] Reaction with the phos-
phine diolefin 13 gave the target complex [(h5-
‡
ˆ
C5Me5)Re(NO)(PPh((CH2)6CH CH2)2)(CO)] BF4 (14) in
high spectroscopic yields. A chromatographic workup afford-
ed analytically pure 14 in 41% yield. Related carbonyl
complexes are reduced by NaBH4 to the corresponding
methyl complexes,[22] which react with strong acids HX to
give species of the formula [(h5-C5R5)Re(NO)(PAr3)(X)]. As
shown in Scheme 5, sequential reactions of 14 with LiAlH4
and (after hydrolysis/extraction) aqueous HCl gave the
Intramolecular reactions: Cyclization between two cis ligands,
each with one olefin. The preceding metatheses involve
similar chiral rhenium fragments that are known to tolerate
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Olefin Metathesis
3931±3950
many types of reactions in their coordination spheres. We
sought to evaluate a wider variety of metal/ligand assemblies.
Thus, for the purposes of testing metatheses between two cis
ligands (Scheme 2C), we turned to six-coordinate octahedral
and four-coordinate square planar substrates. Only macro-
cyclic targets were investigated.
Reactions of pentacarbonyl rhenium halides and phospho-
rus donor ligands (> 2 equiv) give facially-substituted tricar-
bonyl complexes.[26] Accordingly, the reaction of [(CO)5Re-
(Br)] and the phosphine monoolefin 12 in refluxing CHCl3
afforded the target complex fac-[(CO)3Re(Br)(PPh2-
ˆ
(CH2)6CH CH2)2] (21) in 72% yield after workup. As shown
in Scheme 6, a CH2Cl2 solution of 21 (0.0028m) and 1
Figure 2. Structures of rhenium macrocyclic diphosphine complexes (E)-
22 (top) and 23 (bottom). Key bond lengths [Š] and angles [8], (E)-22/23:
Re P1 2.499(2)/2.487(3), Re P2 2.534(2)/2.520(3), Re Br 2.6614(14)/
2.6540(12), Re C39 1.899(10)/1.949(11), Re C40 1.912(11)/2.054(13),
Re C41 1.901(8)/1.936(10), P1-Re-P2 97.48(7)/97.97(8), P1-Re-Br
90.90(6)/89.71(7), P1-Re-C39 88.2(3)/87.6(3), P1-Re-C40 90.0(3)/91.4(3),
P1-Re-C41 178.8(3)/177.9(3), P2-Re-Br 94.04(6)/94.04(7), P2-Re-C39
174.2(3)/174.4(3), P2-Re-C40 91.8(3)/90.8(3), P2-Re-C41 82.7(3)/83.4(3).
NMR spectra of the bulk crystalline sample showed both Z
and E isomers to be present.
Metatheses of coordinatively unsaturated substrates were
investigated. A reaction of platinum cyclooctadiene complex
[(Cl)2Pt(cod)] with 12 gave, in accord with much literature
precedent,[27]
the
bis(phosphine)
complex
cis-
ˆ
[(Cl)2Pt(PPh2(CH2)6CH CH2)2] (24) in 70% yield. The
stereochemistry of 24 and all platinum bis(phosphine) com-
1
pounds below could be assigned from the diagnostic J(P,Pt)
values (cis: 3652 ± 3627 Hz, trans: 2659 ± 2685 Hz).[27] As
shown in Scheme 6, a CH2Cl2 solution of 24 (0.0027m) and 1
(2 mol%) was heated under reflux. Workup gave a substance
whose microanalysis fit the target complex cis-
Scheme 6. Metatheses between two cis-phosphine ligands: macrocyclic
diphosphine chelates. a) H2 (1 atm), cat. 10% Pd/C, toluene/ethanol.
ˆ
(2 mol%) was heated under reflux. Workup gave the seven-
teen-membered macrocyclic chelating diphosphine complex
[(Cl)2Pt(P(Ph)2(CH2)6CH CH(CH2)6P(Ph)2)] (25) in 71%
yield (<2: > 98 Z/E). A second minor species could be
detected by 31P NMR (91:9 in CDCl3 or acetone). Based upon
observations with other PtCl2 adducts of chelating diphos-
phines,[28] we suspected a monomer/dimer mixture, with the
latter involving two mutually-cis bridging diphosphines (26,
Scheme 6).
ˆ
fac-[(CO)3Re(Br)(P(Ph)2(CH2)6CH CH(CH2)6P(Ph)2)] (22)
in an impressive 80% yield (17 ± 20:83 ± 80 Z/E). Hydro-
genation (1 atm, Pd/C) afforded the saturated analogue fac-
[(CO)3Re(Br)(P(Ph)2(CH2)14P(Ph)2)] (23) in 98% yield. The
crystal structures of 22 and 23 were determined (Experimen-
tal Section), and ORTEP diagrams are given in Figure 2. The
crystal of 22 examined contained only the E isomer, although
Indeed, FAB mass spectra showed strong ions with masses
‡
‡
corresponding to (25-Cl) and (26-Cl) (63%, 46%). An
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J. Gladysz et al.
FULL PAPER
osmotic molecular weight determination established that the
major species in solution was 25 (calcd: 830.8, found (CHCl3):
844). A crystal structure (Figure 3, top) showed only (E)-25.
The unit cell dimensions of six additional crystals were
determined, and all were identical. Nonetheless, when crystals
Cl
Cl
S
Pt
Et
Et
S
Cl
Cl
Et
S
Pt
Et
29
S
CH2Cl2
1
Cl
Cl
S
Pt
Et
Et
S
+
S
S
Et
Et
Pt
Cl
Cl
31
32
Cl
Cl
S
Cl
Cl
S
Pt
Pt
S
S
1
CH2Cl2
30
33
Scheme 7. Metatheses between two cis-thioether ligands: macrocyclic
dithioether chelates.
NMR spectra showed mixtures of meso/rac (syn/anti) diaste-
reomers.[29±31]
A CH2Cl2 solution of 29 (0.0016m) and 1 (2 mol%) was
heated under reflux. As shown in Scheme 7, workup gave two
chromatographically separable macrocycles, both of empirical
ˆ
formula [(Cl)2Pt(S(Et)(CH2)6CH CH(CH2)6S(Et))]. The
mass spectrum of the more rapidly eluting complex showed
it to be the monomer 31 (57%, Z/E 21:79). The mass spectrum
of the second complex showed it to be the dimer 32 (24%),[18]
containing a thirty-four membered macrocycle. Due to the
many diastereomers resulting from the four sulfur stereo-
centers, the Z/E ratio was not quantified. Complexes 31 and
32 showed no tendency to interconvert in solution. Hence, the
latter is presumed to be derived from an intermolecular
metathesis.
Figure 3. Structures of platinum macrocyclic diphosphine complexes (E)-
25 (top) and 39 (middle and bottom). Key bond lengths [Š] and angles [8],
(E)-25: Pt P1 2.261(2), Pt-P2 2.2492(13), Pt Cl1 2.337(2), Pt Cl2
2.3586(13), P1-Pt-P2 98.22(5), P1-Pt-Cl2 84.86(5), P1-Pt-Cl1 171.92(4),
P2-Pt-Cl1 89.85(5), P2-Pt-Cl2 175.93(4), Cl1-Pt-Cl2 87.10(5); 39: Pt P1
2.306(2)l, Pt P2 2.299(2), Pt Cl 2.359(2), Pt C21 1.996(7), P1-Pt-P2
172.00(7), Cl-Pt-C21 174.3(2), P1-Pt-Cl 88.67(7), P1-Pt-C21 91.4(2), P2-
Pt-Cl 89.07(7), P2-Pt-C21 91.4(2).
A CH2Cl2 solution of the tert-butyl substituted thio-
ether complex 30 (0.0012m) and 1 (2 mol%) was heated
under reflux. As shown in Scheme 7, workup gave only one
macrocycle,
the
monoplatinum
chelate
cis-[(Cl)2-
ˆ
were dissolved in acetone that had been cooled to 808C, and
31P NMR spectra immediately recorded, both isomers were
present. This indicates either a very rapid equilibrium, or a
devious ability of 26 to disguise itself in the solid sample.
Similar reactions with sulfur donor ligands were investi-
gated. The ethyl and tert-butyl thioethers S(R)(CH2)6-
Pt(S(tBu)(CH2)6CH CH(CH2)6S(tBu))] (33), in 72% yield
(Z/E 16:84).[18] Only a small amount (<4%) of a diplatinum
complex could have gone undetected. Possible reasons for the
higher selectivity with 30 are suggested below.
Intramolecular reactions: Cyclization between two trans
ligands, each with one olefin. Ligands that span trans positions
must by definition be macrocyclic. Most examples involve
diphosphines, an important area that has been recently
reviewed.[28a, 32] In the majority of cases, the diphosphines
are ªpreformedº as opposed to generated by linking two
monophosphines in a metal coordination sphere. We sought
to attempt the synthesis of trans-spanning diphosphines by the
ˆ
CH CH2 (R ˆ Et, 27; R ˆ tBu, 28) were first prepared by
the standard procedures shown in Equation (i). Reactions
with K2[PtCl4] gave, as expected,[29] the bis(thioether) com-
ˆ
plexes cis-[(Cl)2Pt(S(R)(CH2)6CH CH2)2] (R ˆ Et, 29; tBu,
30) in 84 ± 50% yields. As is evident from Scheme 7, the
ligating sulfur atoms in 29 and 30 are stereocenters. In
agreement with an extensive literature of similar complexes,
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Olefin Metathesis
3931±3950
ˆ
route in Scheme 2D. If successful, this would represent the
first monophosphine-linking protocol yielding a hydrocarbon
tether.
The phosphine monoolefin 12, rhodium complex [Rh(m-
Cl)(COD)]2, and CO were combined under conditions known
to give bis(phosphine) complexes trans-[(Cl)(CO)Rh(L)2].[33]
(C6F5)Pt(PPh2(CH2)6CH CH2)2] (37) in 79% yield. As shown
in Scheme 8, a CH2Cl2 solution of 37 (0.0025m) and 1
(6 mol%; added in two portions) was heated under reflux.
Alumina filtration gave the target macrocycle trans-
ˆ
[(Cl)(C6F5)Pt(P(Ph)2(CH2)6CH CH(CH2)6P(Ph)2)] (38) in
90% yield (Z/E 17:83), which gave correct microanalyses.
Depending upon how the filtration was conducted, samples
contained up to 15% of a second species, as assayed by 31P
NMR spectroscopy. This was provisionally assigned to a
diplatinum by-product derived from intermolecular meta-
thesis.
ˆ
Workup afforded trans-[(Cl)(CO)Rh(PPh2(CH2)6CH CH2)2]
(34) in 79% yield. As shown in Scheme 8, a CH2Cl2 solution of
CO
Rh
CO
Rh
1
Ph2P
PPh2
Ph2P
PPh2
Reactions of 38 and H2 (1 atm) in the presence of 10% Pd/
catalyst gave the saturated macrocycle trans-
CH2Cl2
C
Cl
Cl
[(Cl)(C6F5)Pt(P(Ph)2(CH2)14P(Ph)2)] (39). Yields of analyti-
cally pure material ranged from 94% (with up to 15% of a by-
product by 31P NMR) to 72% (no by-product). A crystal
structure was determined, and two views are given in Figure 3
(middle and bottom). The second highlights a stacking
interaction involving the pentafluorophenyl ligand and a
phenyl group on each phosphorus. It is now well established
that p -C6H5/-C6F5 interactions are attractive and a driving
force in many crystallizations.[36]
34
35
a)
F
F
F
F
CO
Rh
F
Ph2P
Pt
PPh2
Ph2P
PPh2
Intramolecular reactions: Cyclization involving two or more
ligands, each with two olefins. We next sought to test the
feasibility of polymacrocyclization reactions, as exemplified in
Scheme 2E. The simplest version would involve two ligands
that each contain two terminal olefins. One such metathesis
has been communicated.[6b] This unexpectedly selective pro-
cess exhibits so many fascinating nuances that it will be
reported as a part of a separate, long-term study. Thus, we
conclude this paper with a reaction at the next higher level of
complexityÐa substrate featuring three facially disposed
ligands, each bearing two terminal olefins. In this case, an
extensive mixture of trimacrocyclic products is obtained.
The reaction of tungsten propionitrile complex fac-
[(CO)3W(NCCH2CH3)3] (40)[37] and phosphine diolefin 13
gave, in accord with much literature precedent,[38] the tris-
Cl
Cl
36
37
1
CH2Cl2
F
F
F
F
F
F
F
F
F
F
Ph2P
Pt
PPh2
Ph2P
Pt
PPh2
b)
Cl
Cl
38
39
ˆ
(phosphine) complex fac-[(CO)3W(PPh((CH2)6CH CH2)2)3]
Scheme 8. Metatheses between two trans-phosphine ligands: trans-span-
ning macrocyclic diphosphine chelates. a) H2 (5 atm), cat. [Rh(PPh3)3(Cl)],
toluene; b) H2 (1 atm), cat. 10% Pd/C, ethanol/ClCH2CH2Cl.
(41) in 71% yield. As shown in Scheme 9, a CH2Cl2 solution of
ˆ
41 (0.00042m) and 1 (9 mol% or 3 mol% per product C C)
was heated under reflux. Chromatography gave a sample of
ˆ
empirical formula [(CO)3W(P(Ph)((CH2)6CH )2)3] (42) in
34 (0.0027m) and 1 (5 mol%) was heated under reflux.
Chromatography gave the target macrocycle trans-
83% yield. NMR spectra indicated that all terminal olefins
had been replaced by disubstituted olefins, and a mass
spectrum showed an intense molecular ion (100%).[18] The
pattern of the isotope envelope (m/z 1173 ± 1179) agreed
perfectly with that calculated. HPLC showed three over-
lapping regions of partially resolved peaks. Three limiting
structures are given in Scheme 9: 42a, with one triphosphine,
42b, with one diphosphine and one monophosphine, and 42c,
with three monophosphines. We conjectured that these might
correspond to the three HPLC regions. The mass spectrum
showed ions for each type of ligand (3 Â 10%).
ˆ
[(Cl)(CO)Rh(P(Ph)2(CH2)6CH CH(CH2)6P(Ph)2)] (35) in
an astoundingly high 83% yield (Z/E 17:83). A reaction of
35 and H2 (5 atm) in the presence of Wilkinsonꢀs catalyst
afforded the saturated trans-spanning diphosphine complex
trans-[(Cl)(CO)Rh(P(Ph)2(CH2)14P(Ph)2)] (36) in high spec-
troscopic yields. However, due to several minor workup
complications (see Experimental Section), analytically pure
product could only be obtained in 55% yield.
In an attempt to obtain a crystalline trans-spanning
diphosphine complex, we returned to platinum compounds.
First, the pentafluorophenyl platinum dihydrothiophene
(SR2) complex [Pt(m-Cl)(C6F5)(SR2)]2 and 12 were combined
under conditions known to give bis(phosphine) complexes
trans-[(Cl)(C6F5)Pt(L)2].[34, 35] Workup gave trans-[(Cl)-
Two complexes could be crystallized from this mixture. The
crystal structures were determined, and are illustrated in
Figure 4. Both feature a forty-five membered macrocyclic
tridentate triphosphine with three E C C linkages (42a',
42a''). They differ in phosphorus stereochemistry. The first
ˆ
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J. Gladysz et al.
FULL PAPER
Ph
Ph
CO
W
P
P
OC
CO
P
Ph
41
83%
(all
1
cyclized
material)
Ph
Ph
Ph
Ph
Ph
Ph
CO
W
CO
W
CO
W
P
P
P
P
P
P
OC
OC
CO
CO
OC
CO
P
P
P
Ph
Ph
Ph
42a
42c
42b
a)
corresponding saturated compounds (94%)
(43)
Scheme 9. Metatheses between three fac-phosphine ligands: polymacrocyclizations. a) H2 (6 atm), cat. [Rh(PPh3)3(Cl)], toluene.
has all three PPh groups anti to the W(CO)3 moiety, while the
second has one PPh group syn. Considering all Z/E and syn/
Discussion
anti permutations, there are sixteen possible stereoisomers of
42a. Complexes 42b and 42c can have as many as eighteen
and four stereoisomers, respectively (the diphosphine in 42b
has three possible PPh orientations). The HPLC and 31P NMR
data suggested that a majority of these 38 species were
present.
Scope of title reaction: The preceding data establish the broad
applicability of Grubbsꢀ catalyst 1 for effecting olefin
metatheses in metal coordination spheres. Our examples
involve neutral and charged, coordinatively saturated and
unsaturated, and octahedral and square-planar rhenium,
platinum, rhodium, and tungsten complexes with cyclopenta-
dienyl, phosphine, and thioether ligands that contain terminal
olefins. The previously described metatheses in Scheme 1
feature olefin-containing Fischer carbene, ferrocene, and
tripyridyl-based ligands. More recent reports that further
expand synthetic utility are summarized in Scheme 10.
Scheme 10B depicts a family of cross-metatheses in ferro-
cene coordination spheres. Together with other examples,[3a]
these can be viewed as conceptual extensions of the inter-
molecular homometatheses in Schemes 2A and 3.
Schemes 10C, 10D, and 1A involve the formation of medium
or small rings within ligands, thus constituting examples of
Scheme 2B. We find the excellent yield with the highly
Complexes 42 and H2 (ca. 6 atm) were reacted in the
presence of Wilkinsonꢀs catalyst. Workup gave the corre-
sponding mixture of saturated complexes (43) in 94% yield,
1
as assayed by mass spectrometry and H NMR spectroscopy.
However, the HPLC trace and 31P NMR spectrum remained
complex, and further purification attempts were not success-
ful. We note in passing that analogues of 42a with much
smaller ring sizes have been prepared by free radical
cyclizations of M(CO)3 (M ˆ Cr, Mo, W) adducts of allyl or
[39, 40]
ˆ
homoallyl monophosphines H2C CH(CH2)nPH2.
In
some cases, the new tridentate triphosphines have been
detached from the metal.[39c,d]
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Olefin Metathesis
3931±3950
Figure 4. Structures of tungsten trimacrocyclic triphosphine complexes
42a' (top) and 42a'' ´ (C6H14)0.5 (bottom, solvate omitted). Key bond lengths
[Š] and angles [8], 42a': W P 2.545(2), W C1 1.938(10), P-W-P 99.29(7),
P-W-C1 84.0(3), P-W-C1a 89.7(3), P-W-C1b 169.8(3); 42a'' ´ (C6H14)0.5
:
Scheme 10. Additional examples of olefin metathesis in metal coordina-
tion spheres.
W P1 2.537(3), W P2 2.554(2), W P3 2.556(3), W C1 1.969(9), W C2
1.982(10), W C3 1.981(9), P1-W-P2 96.51(8), P1-W-P3 95.69(9), P1-W-C1
82.8(2), P1-W-C2 171.4(3), P1-W-C3 92.0(3), P2-W-P3 96.13(9), P2-W-C1
89.7(3), P2-W-C2 83.9(3), P2-W-C3 170.2(3), P3-W-C1 174.1(3), P3-W-C2
92.8(3), P3-W-C3 87.8(3).
PCy3 (4 equiv, CDCl3) gave the known compound trans-
[(Cl)(CO)Rh(PCy3)2].[41]
All of our reactions give internal olefins, which are much
less reactive towards the chain-carrying ruthenium alkylidene
than terminal olefins.[42] We therefore presume that they are
under kinetic control. However, we did not monitor product
Z/E ratios as a function of time, or attempt to anneal or
equilibrate products by treating purified samples with 1. This
represents a possible approach to enhancing the selectivities,
such as with the reaction in Scheme 9. Some of the new
second-generation ruthenium catalysts appear particularly
promising for such purposes.[8, 43, 44]
functionalized 1,3-diene iron tri(carbonyl) in Scheme 10C
particularly noteworthy. The two-fold metathesis of the
diolefinic pyridine ligands in Scheme 10A leads to a novel
doubly trans-spanning macrocycle. This can be viewed as a
conceptual extension of the monocyclizations in Schemes 2D
and 8. However, this system is geometrically predisposed
towards trans cyclization, unlike the substrates in Scheme 8,
which are further analyzed below.
Although the yields of our metathesis reactions are high,
they are in most cases unoptimized (particularly Schemes 3 to
7). The catalyst loadings are typical of those used with organic
substrates. We view the apparent absence of side reactions
involving the chain-carrying ruthenium alkylidene as remark-
able. Deactivation was sometimes observed, but this could be
remedied by the portion-wise addition of 1. Some metatheses
of rhodium complex 34 (Scheme 8) gave minor by-products
(31P NMR), which seem to be in part derived from the PCy3
that dissociates from 1. An independent reaction of 35 and
Why are the macrocyclizations so successful? The uniformly
high yields of the many types of intramolecular macrocycliza-
tions (Schemes 5 to 9) deserve analysis. Substrate concen-
trations range from 0.0028mÐin our view, not particularly
diluteÐto 0.00042m, which corresponds to 0.131 g of 41 in
250 mL of CH2Cl2. Hence, factors or properties that enhance
the competitiveness of intramolecular versus intermolecular
reactions appear likely.
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J. Gladysz et al.
FULL PAPER
Fürstner has compared metatheses of a,w-diolefins that
lack functionality in the backbone to those with various
Lewis-basic functional groups. To account for the much higher
yields of simple monomeric macrocycles with the latter,
transient binding of the chain-carrying ruthenium alkylidene
was proposed.[25] In this context, consider the diolefins 14 and
15 in Scheme 5. Both lack binding sites in the intervening
(CH2)6P(CH2)6 chain. External to this assembly, the nitrosyl,
carbonyl, and chloride ligands are possible candidates. How-
ever, the first two are very feeble Lewis bases. Although the
chloride ligand can bind a second metal,[45] 14 shows that it is
not required for macrocyclization.
It is well known that when geminal dialkyl groups are
introduced on a methylene chain (e.g., a -CH2CR2CH2CH2-
moiety) intramolecular a,w-cyclizations are promoted.[46, 47]
The alkyl groups render the energies of anti and gauche
conformations much closer, as illustrated in Scheme 11A ± B
(I/II vs. III/IV). In all carbocycles (and the precursor
transition states), gauche segments are mandatory, as easily
identified in the above crystal structures. We propose that in
14 and 15, the phenyl and rhenium groups on phosphorus play
roles equivalent to those of geminal dialkyl groups in
carbocyclic systems. As illustrated in Scheme 11C, the energy
of the macrocyclization-friendly gauche conformer VI (CH2
gauche to phenyl and CH2 groups) might even be lower than
that of the anti isomer V (CH2 gauche to phenyl and LnM
groups). An alternative but less precise formulation would be
that bulky metal fragments restrict the conformational space
and freedom of coordinated ligands, such that the terminal
olefins in complexes such as 14 and 15 have a higher
probability of being close to each other.
A. Model equilibrium I
CH2
CH2
H
H
H
H
H
H
H
H
CH2
CH2
gauche
larger energy
difference
anti
I
II
B. Model equilibrium II
R
CH2
CH2
H
R
H
H
R
H
R
CH2
CH2
gauche
IV
smaller energy
difference
anti
III
C. Equilibrium in monophosphine complexes (14, 15)
MLn
P
CH2
P
H
H
H
H
?
Ph
CH2
LnM
Ph
CH2
CH2
anti
V
gauche conformer
possibly favored
gauche
VI
D. Representative equilibrium in cis-bis(phosphine) complexes (21, 24)
With the cis-bis(phosphine) complexes 21 and 24 (Scheme 6),
the metal becomes part of the macrocyclic ring. Thus, con-
formations of the MPPh2CH2CH2 segments must be analyzed,
and two of many possibilities are depicted in Scheme 11D.
Relative to model compounds with MPH2CH2CH2 or MCH2-
CH2CH2 segments, the phosphorus phenyl groups should
increase the fraction of molecules with cyclization-favorable
gauche conformations (e.g., VIII). Since 24 gives monoplatinum
and diplatinum macrocycles that appear to be in equilibrium
(25, 26), we do not rigorously know if intramolecular meta-
thesis is kinetically preferred. However, the cis-bis(thioether)
complex 29 yields monoplatinum and diplatinum macrocycles
that are not in equilibrium (31, 32; Scheme 7). This shows that
intramolecular macrocyclization of 29 is preferred. We
presume that 24 exhibits analogous selectivity.
Ph
P
Ph
P
Ph
P
Ph
P
H
CH2
H
CH2
Ph
H2C
Ph
H
H
CH2
Ph
?
Ph
M
M
H
H
H
H
anti/anti
gauche/anti
VII
VIII
E. Representative equilibrium in cis-bis(thioether) complexes (29, 30)
H2C
H
H
CH2
R
H
R
CH2
H
CH2
R
?
S
S
S
S
R
Pt
Pt
H
H
H
H
: K larger
R = Et : K smaller
gauche/anti
anti/anti
R = tBu
X
IX
In contrast to 21 and 24, the cis-bis(thioether) complexes 29
and 30 lack geminal groups. Since they give predominantly
intramolecular macrocyclization (30, tBu > 29, Et), additional
factors that promote ring formation are likely (and further-
more operative with 21 and 24). We feel it would be
premature to speculate about these at this time. However,
the higher proportion of intramolecular metathesis with 30
can be rationalized. In an anti Pt-SR-CH2-CH2 conformation,
the R group is gauche to a hydrogen atom and a methylene
group (IX, Scheme 11E). In a gauche conformation (X), the R
group is gauche to two hydrogen atoms. Hence, a tert-butyl
group should increase the fraction of molecules with gauche
conformations.
F. Representative equilibrium in trans-bis(phosphine) complexes (34, 37)
Ph
H
H
H
H
Ph
Ph
Ph
Ph
CH2
H
H
Ph
Ph
?
H2C
P
M
P
CH2
H
P
M
P
CH2
Ph
H
gauche/anti
anti/anti
XI
XII
Scheme 11. Conformational factors in macrocyclizations.
With the trans-bis(phosphine) complexes 34 and 37
(Scheme 8), the phenyl groups will (as with 21 and 24)
increase the fraction of gauche M-PPh2-CH2-CH2 conforma-
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Olefin Metathesis
3931±3950
tions relative to those in suitable models. As shown in
Scheme 11F, conformer XII should gain at the expense of XI.
However, there are many possible conformations about the
metal phosphorus bonds besides those shown, and the trans
chains must localize on the same side of the metal square
plane. A greater phosphorus phosphorus bond length must
be traversed than in the preceding examples, with increased
potential for van der Waals interactions with the metal frag-
ment. Thus, we find the success of these intramolecular
macrocyclizations particularly surprising. With 37, a -C6H5/
-C6F5 stacking interaction as in crystalline 39 (Figure 3) might
provide a preorganizational benefit.[36] However, this would
be absent in 34. As communicated earlier,[6b] it is furthermore
possible to effect a double macrocyclization, akin to that of
the preorganized ortho-disubstituted pyridine complex in the
Scheme 10A. Accordingly, the scope of and possible driving
forces for such trans-macrocyclizations remain under active
investigation.[48]
as the methylene chain extends from each phosphorus. Both
Pt-P-CH2-CH2 conformations are analogous to the gauche
linkage in XII (Scheme 11F).
When molecules are viewed at van der Waals radii, the
macrocycles contain little ªempty spaceº. Another common
feature is that there are no marked distortions in bond lengths
or angles about the metals. For example, the trans-spanning
ligand in 22 gives a P-Pt-P bond angle (172.00(7)8) close to
1808, and comparable to the Cl-Pt-C angle (174.3(2)8).
Metal ligand bonds have lower bending force constants than
sp3 ± sp3 carbon carbon bonds. Hence, this is consistent with
little or no bond or angle strain within the seventeen-
membered ring (normalized to the number of atoms). Since
numerous non-macrocyclic structural models for all of the
preceding compounds are readily obtained from the Cam-
bridge crystallographic data base, we do not provide a list of
references or otherwise discuss the routine metrical param-
eters summarized in the captions.
Macrocycle structures: The crystal structures in Scheme 1 ± 4
exhibit a variety of macrocycle conformations, aspects of
which are relevant to the analyses in the preceding section.
For example, the Z- and E isomers of the fifteeen-membered
macrocycle 17 (Figure 1) feature gauche conformations of the
type VI (Scheme 11C) about all four CH2P(Ph)(Re)CH2CH2
segments. The overall C34-C33-C32-C31-P-C21-C22-C23-
C24-C25-C26 conformations are quite similar, with gauche
butane segments at C21-C22-C23-C24, C22-C23-C24-C25,
Summary and Prospective
We have demonstrated the viability of Grubbsꢀ catalyst 1 for
the construction of numerous types of acyclic, cyclic, and
macrocyclic inorganic and organometallic compounds from
easily accessed precursors. Intramolecular metatheses are
always more efficient than intermolecular metatheses, even
under only modestly dilute conditions. Many of the macro-
cycles are topologically novel, and most metatheses are
remarkably selective. As one proceeds through the increas-
ingly complex paradigm in Scheme 2, product mixtures are
encountered only at the stage 2E. These are tractable in at
least some cases.[6b] However, Scheme 9, which represents a
still higher level of complexity, gives an intractable mixture of
seemingly every possible isomer of 42a ± c, from which we
were fortunate to acquire at least some meaningful data.
Nonetheless, this constitutes an efficient synthesis of a
combinatorial library, an area in which olefin metathesis is
seeing increasing application.[49]
The preceding data also leave a number of open questions
that will make attractive themes for future research. For
example, how are the macrocyclizations in Schemes 5 to 9
affected by the lengths of the methylene chains and the
presence of substitutents and/or heteroatoms? Do newer
second-generation ruthenium metathesis catalysts effect sig-
nificant improvements? Can chiral metathesis catalysts[50]
effect kinetic resolutions of chiral organometallic substrates
(Schemes 3 ± 5), or enantioselective syntheses of chiral prod-
ucts from achiral substrates (e.g., certain isomers of 42a ± b)?
Most importantly, the stage is now firmly set for the wide-
spread and systematic application of olefin metathesis in the
targeted synthesis of complex organometallic systems. Spe-
cific applications involving multistep sequences will be
reported in the near future.[51]
ˆ
and C23-C24-C25-C26. The C C linkages (C27 C37) initiate
four carbon sequences where the conformations are distinctly
different.
The seventeen-membered macrocycles in (E)-22 (Figure 2)
and (E)-25 (Figure 3) areÐdespite the difference in metal
coordination numbersÐvery similar with respect to the P1-M-
P2 and phosphorus phenyl ring conformations. The Pt-PPh2-
C14-C13 and Pt-PPh2-C1-C2 conformations in (E)-25 are
analogous to the gauche and anti segments in VIII
(Scheme 11D), respectively. The Re-PPh2-C14-C13 and Re-
PPh2-C1-C2 conformations in (E)-22 are both gauche. The
C14-C13-C12-C11-C10-C9 linkages are quite similar in (E)-22
and (E)-25 (anti, gauche, anti butanes). However, the C9 C8
conformations (the vinyl linkages) differ by approximately
1808, resulting in distinctly different return paths to phospho-
rus P1. The saturated macrocycle 23 is virtually identical to
(E)-22 over the C2-C1-P1-Re-P2-C14-C13-C12-C11-C10-C9
moiety.
Complex 42a' (Figure 4) features a three-fold rotational
symmetry axis, which renders the macrocyclic rings equiva-
lent. The ring sizes and olefin geometries are the same as in
(E)-22 and (E)-25, but since there is only one phenyl group on
each phosphorus, comparisons are not as meaningful. There is
one gauche butane segment on one side of the olefin (C11-
ˆ
C12-C13-C14), gauche CH-CH2-CH2-CH2 conformations on
each side of the olefin, and only anti butane segments on the
path back to tungsten. Every macrocyclic ring in the lower-
symmetry isomer 42a'' has a unique conformation. The
saturated trans-spanning macrocycle in 39 (Figure 3) is
disordered, but the major isomer exhibits a very symmetrical
conformation with anti, anti, anti, and gauche butane segments
Experimental Section
General data: All reactions except thioether syntheses were conducted
under N2 (or H2) atmospheres. Chemicals were treated as follows: acetone,
2-butanone, and CHCl3, distilled from anhydrous CaSO4; THF, diethyl
ether (ether), benzene, and toluene, distilled from Na/benzophenone;
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J. Gladysz et al.
FULL PAPER
CH2Cl2 and C6H5Cl distilled from CaH2 and then P2O5; pentane and
hexane, distilled from P2O5; ClCH2CH2Cl (99%, Fluka), DMF (99%,
Fluka), methanol and ethanol, used as received; CDCl3, vacuum trans-
ferred from CaH2 or P2O5; [D6]benzene, vacuum transferred from Na;
nBuLi (Acros, 2.5 or 1.6m in hexanes), standardized;[52] K2PtCl4 (Strem),
24H, 12CH2), 0.93 (d, 3J(H,P) ˆ 6 Hz, 6H, 2ReCH3); 13C{1H} NMR
(75 MHz, CDCl3, 208C): d ˆ 136.5 (d, 1J(C,P) ˆ 51 Hz, i-Ph), 133.6 (d,
4
3
2J(C,P) ˆ 11 Hz, o-Ph), 129.7 (d, J(C,P) ˆ 2 Hz, p-Ph), 128.1 (d, J(C,P) ˆ
10 Hz, m-Ph), 112.7 (s, iC5H4R), 91.7, 88.7, 86.4, 84.0 (4s, other C5H4R), 30.9
(s, CH2), 29.6 (s, 2 Â intensity, CH2), 29.5 (s, CH2), 29.4 (s, CH2), 29.3 (s,
CH2), 28.1 (s, CH2), 32.9 (d, 2J(C,P) ˆ 7 Hz, ReCH3); 31P{1H} NMR
(121 MHz, CDCl3, 208C): d ˆ 26.1 (s); IR (KBr): nÄ ˆ 1621 (NO) cm 1; MS
ˆ
water-insoluble residue removed by filtration; Br(CH2)6C CH2 (4; 97%,
Aldrich or Fluka), PPh2H (Aldrich), PPhH2 (97%, Fluka),
‡
ˆ
PPh(CH2CH CH2)2 (95%, Aldrich), HSEt (Aldrich), NaS-tBu (Aldrich),
(FAB, 3-NBA/CH2Cl2): m/z (%): 1312 (12) [M] ; elemental analysis calcd
ˆ
LiAlH4 (97%, Fluka), TfOH (97%, Merck), [Ru( CHPh)(PCy3)2(Cl)2] (1,
(%) for C62H72N2O2P2Re2 (1311.64): C 56.78, H 5.53; found: C 56.87, H 5.70.
Strem), [Rh(PPh3)3(Cl)] (Strem), and Pd/C (10%, Lancaster or Acros),
used as received.
5
‡
ˆ
[(h -C5H5)Re(NO)(PPh3)(SCH2CH CHCH2)] TfO (9): A Schlenk flask
5
‡
ˆ
was charged with [(h -C5H5)Re(NO)(PPh3)(S(CH2CH CH2)2)] TfO
(8;[15] 0.242 g, 0.300 mmol) and CH2Cl2 (140 mL). Another Schlenk flask
was charged with 1 (0.005 g, 0.006 mmol, 2 mol%) and CH2Cl2 (5 mL). The
latter solution was added by cannula to the former with stirring. The
mixture was heated under reflux (3 h) and turned light brown. A small
amount of activated charcoal was added. The suspension was swirled and
filtered through a Celite plug (2 cm). Solvent was removed by rotary
evaporation. The residue was dissolved in acetone and layered with ether.
After 48 h, red prisms of 9 were collected by filtration and dried under oil
pump vacuum (0.175 g, 0.225 mmol, 75%). M.p. 1918C (decomp); 1H NMR
(300 MHz, CDCl3, 208C): d ˆ 7.57 ± 7.54 (m, 9H of 3Ph), 7.36 ± 7.31 (m, 6H
of 3Ph), 5.92 (brs, 2H, SCH2CH), 5.60 (s, 5H, C5H5), 3.75 (m, 4H,
2SCHH'); 13C{1H} NMR (75 MHz, CDCl3, 208C): d ˆ 133.5 (d, 2J(C,P) ˆ
11 Hz, o-Ph), 132.7 (d, 1J(C,P) ˆ 56 Hz, i-Ph), 132.0 (d, 4J(C,P) ˆ 2 Hz, p-
Ph), 130.0 (d, 3J(C,P) ˆ 11 Hz, m-Ph), 127.6 (s, SCH2CH), 93.4 (s, C5H5),
54.5 (s, SCH2); 31P{1H} NMR (121 MHz, CDCl3, 208C): d ˆ 11.5 (s); IR
(CH2Cl2/Nujol): nÄ ˆ 1711/1708 (NO) cm 1; MS (FAB, 3-NBA/CH2Cl2): m/z
IR spectra were recorded on Mattson Polaris FT or ASI React-IR 1000
spectrometers. NMR spectra were obtained on Varian 300 MHz or Jeol
400 MHz spectrometers. Mass spectra were recorded on Finnigan MAT 95
or Micromass Zabspec high resolution instruments. Microanalyses were
conducted by Atlantic Microlab or with a Carlo Erba EA1110 instrument
(in-house). Osmotic molecular weights were determined by Galbraith.
5
ˆ
[(h -C5H4(CH2)6CH CH2)Re(NO)(PPh3)(CH3)] (5): A Schlenk flask was
charged with [(h5-C5H5)Re(NO)(PPh3)(CH3)] (2;[9] 0.553 g, 0.989 mmol)
and THF (20 mL) and cooled to 308C. Then nBuLi (2.5m, 1.10 mL,
2.7 mmol) was added dropwise with stirring over 5 min.[10] After 5 h, 4
(0.43 mL, 2.56 mmol) was added with stirring. After 18 h, solvent was
removed by oil pump vacuum. The red oil was placed on top of a Celite/
silica plug (2 cm each above a frit). The red material was rinsed through the
plug with toluene. The sample was taken to dryness by oil pump vacuum.
Column chromatography (silica gel, 20:1 v/v hexane/THF) gave two
partially resolved bands (5, 2). The forerun of the first was collected and
dried by oil pump vacuum to give 5 as a red oil (0.358 g, 0.535 mmol, 54%).
1H NMR (300 MHz, CDCl3, 208C): d ˆ 7.44 ± 7.37 (m, 15H, 3Ph), 5.78 (m,
‡
‡
(%): 630 (100) [M] , 544 (59) [M SCH2CH CHCH2] ; elemental
analysis calcd (%) for C28H26F3NO4PS2Re (778.82) C 43.18, H 3.36; found:
C 43.16, H 3.35.
ˆ
ˆ
1H, CH ), 5.21 (m, 1H of C5H4), 4.93 (m, 2H, CH2), 4.61, 4.56, 4.10 (3m,
ˆ
5
‡
3H of C5H4), 2.18 (m, 2H, C5H4CH2), 2.00 (m, 2H, CH2CH ), 1.54 ± 1.21
ˆ
[(h -C5H5)Re(NO)(PPh3)(PMe(CH2CH CH2)2)] TfO (10a): A Schlenk
flask was charged with 2 (0.759 g, 1.36 mmol) and C6H5Cl (25 mL) and
cooled to 458C. Then TfOH (0.120 mL, 1.36 mmol) was added with
stirring. After 5 min, the cold bath was removed. After 20 min,
(m, 8H, 4CH2), 0.90 (d, 3J(H,P) ˆ 6 Hz, 3H, ReCH3); 13C{1H} NMR
(75 MHz, CDCl3, 208C): d ˆ 139.1 (s, CH ), 136.5 (d, 1J(C,P) ˆ 51 Hz, i-
ˆ
Ph), 133.6 (d, 2J(C,P) ˆ 11 Hz, o-Ph), 129.8 (d, 4J(C,P) ˆ 3 Hz, p-Ph), 128.1
(d, 3J(C,P) ˆ 10 Hz, m-Ph),[53] 114.2 (s, CH2), 112.6 (s, iC5H4R), 91.8, 88.8,
ˆ
[56]
ˆ
PMe(CH2CH CH2)2 (ca. 4.0 mmol from a ca. 90% pure ether solution
)
ˆ
86.5, 84.1 (4s, other C5H4R), 33.7 (s, CH2CH ), 30.9 (s, CH2), 29.2 (s, CH2),
was added. After 16 h, the yellow solution was concentrated to about
15 mL by oil pump vacuum. Hexane (50 mL) was added dropwise giving an
oil, which was stirred (0.5 h) and then triturated. The solid was collected by
filtration, washed with pentane (50 mL), ether (50 mL), and pentane
(10 mL), and dried by oil pump vacuum (3 d) to give 10a as a bright yellow
microcrystalline powder (1.021 g, 1.244 mmol, 92%). M.p. 177 ± 1808C;
1H NMR (300 MHz, CDCl3, 208C): d ˆ 7.55 ± 7.25 (m, 15H, 3Ph), 5.61 (m,
28.9 (s, CH2), 28.8 (s, CH2), 28.0 (s, CH2), 32.9 (d, 2J(C,P) ˆ 7 Hz,
ReCH3); 31P{1H} NMR (121 MHz, CDCl3, 208C): d ˆ 25.7 (s); IR (KBr):
nÄ ˆ 1633 (NO) cm 1; MS (FAB, 3-NBA/CH2Cl2): m/z (%): 669 (100) [M] ,
‡
‡
654 (17) [M CH3] ; elemental analysis calcd (%) for C32H37NOPRe
(668.83): C 57.47, H 5.58; found: C 57.26, H 5.65.
5
5
ˆ
[(H3C)(Ph3P)(ON)Re(h -C5H4(CH2)6CH CH(CH2)6-h -C5H4)Re(NO)-
(PPh3)(CH3)] (6): Schlenk flask was charged with (0.380 g,
ˆ
ˆ
2H, 2CH ), 5.51 (s, 5H, C5H5), 5.30 ± 4.92 (m, 4H, 2 CH2), 2.94 ± 2.33 (m,
4H, 2PCHH'), 1.33 (d, 2J(H,P) ˆ 9 Hz, 3H, PCH3); 13C{1H} NMR
(75 MHz, CDCl3, 208C): d ˆ 134.1 (d, 1J(C,P) ˆ 55 Hz, i-Ph), 133.2 (d,
A
5
0.568 mmol), 1 (0.015 g, 0.018 mmol, 3 mol%), and CH2Cl2 (60 mL). The
solution was heated under reflux (1.5 h). Solvent was removed by rotary
evaporation. The brown foam was dissolved in a minimum of CH2Cl2. The
solution was rinsed through a Celite/silica plug (1 and 2 cm above a frit).
Solvent was removed by oil pump vacuum to give 6 as an orange solid
(0.355 g, 0.271 mmol, 95%; Z/E 23:77[54, 55a]). M.p. 728C; 1H NMR
(300 MHz, CDCl3, 208C): d ˆ 7.42 ± 7.35 (m, 30H, 6Ph), 5.35 (m, 2H,
2J(C,P) ˆ 11 Hz, o-Ph), 131.6 (d, J(C,P) ˆ 1 Hz, p-Ph), 129.2 (d, J(C,P) ˆ
4
3
11 Hz, m-Ph), 128.8 (d, J(C,P) ˆ 9 Hz, CH ), 128.7 (d, 2J(C,P) ˆ 9 Hz,
2
ˆ
3
3
ˆ
ˆ
ˆ
C'H ), 121.3 (d, J(C,P) ˆ 6 Hz, CH2), 121.2 (d, J(C,P) ˆ 6 Hz, C'H2),
92.0 (s, C5H5), 36.0 (d, 1J(C,P) ˆ 33 Hz, PCH2), 35.1 (d, 1J(C,P) ˆ 33 Hz,
PC'H2), 12.9 (d, J(C,P) ˆ 35 Hz, PCH3); 31P{1H} NMR (121 MHz, CDCl3,
1
ˆ
208C): d ˆ 12.2 (d, 2J(P,P) ˆ 12 Hz, PPh3),
27.8 (d, 2J(P,P) ˆ 12 Hz,
CH CH), 5.21, 4.61, 4.56, 4.10 (4m, 4 Â 2H, 2C5H4), 2.19 (m, 4H,
ˆ
PMeR2); IR (KBr): nÄ ˆ 1709 (NO) cm 1; elemental analysis calcd (%) for
2C5H4CH2), 1.94 (m, 4H, 2CH2CH ), 1.54 ± 1.21 (m, 16H, 8CH2), 0.89
3
(d, J(H,P) ˆ 6 Hz, 6H, 2ReCH3); 13C{1H} NMR (75 MHz, CDCl3, 208C):
C31H33F3NO4P2SRe (820.86): C 45.36, H 4.05; found: C 45.27, H 4.15.
d ˆ 136.5 (d, 1J(C,P) ˆ 51 Hz, i-Ph), 133.6 (d, J(C,P) ˆ 11 Hz, o-Ph), 130.3
5
‡
2
ˆ
[(h -C5H5)Re(NO)(PPh3)(PPh(CH2CH CH2)2)] TfO (10b): Complex 2
4
3
ˆ
(s, CH CH), 129.7 (d, J(C,P) ˆ 2 Hz, p-Ph), 128.1 (d, J(C,P) ˆ 10 Hz, m-
(1.507 g, 2.701 mmol), C6H5Cl (25 mL), TfOH (0.480 g, 3.20 mmol), and
Ph), 112.7 (s, iC5H4R), 91.7, 88.7, 86.4, 84.0 (4s, other C5H4R), 32.6 (s,
ˆ
PPh(CH2CH CH2)2 (0.760 g, 4.00 mmol) were combined at 158C in a
ˆ
CH2CH , E), 30.9 (s, CH2), 29.5 (s, CH2), 29.3 (s, CH2), 28.9 (s, CH2), 28.0 (s,
procedure analogous to that for 10a. An identical workup (final product
wash with pentane) gave 10b as a bright yellow microcrystalline powder
(1.221 g, 1.383 mmol, 51%). M.p. 138 ± 1408C; 1H NMR (400 MHz, CDCl3,
CH2), 32.9 (d, 2J(C,P) ˆ 7 Hz, ReCH3); 31P{1H} NMR (121 MHz, CDCl3,
208C): d ˆ 26.0 (s); IR (KBr): nÄ ˆ 1621 (NO) cm 1; MS (FAB, 3-NBA/
‡
‡
CH2Cl2): m/z (%): 1310 (6) [M] , 1295 (2) [M CH3] ; elemental analysis
calcd (%) for C62H70N2O2P2Re2 (1309.61): C 56.86, H 5.39; found: C 56.52,
H 5.64.
ˆ
328C): d ˆ 7.55 ± 7.01 (m, 20H, 4Ph), 5.53 (m, 2H, 2CH ), 5.43 (s, 5H,
C5H5), 5.32 ± 5.08 (m, 4H, 2 CH2), 3.32 ± 2.74 (m, 4H, 2PCHH'); 13C{1H}
ˆ
NMR (100 MHz, CDCl3, 328C): d ˆ 134.0 (d, 1J(C,P) ˆ 55 Hz, i-PPh3),
133.2 (d, 2J(C,P) ˆ 11 Hz, o-PPh3), 133.0 (d, 1J(C,P) ˆ 56 Hz, i-PPhR2),
[(H3C)(Ph3P)(ON)Re(h5-C5H4(CH2)14-h5-C5H4)Re(NO)(PPh3)(CH3)]
2
(7):
A
Schlenk flask was charged with
6
(0.174 g, 0.133 mmol),
130.3 (d, J(C,P) ˆ 11 Hz, o-PPhR2), 131.5 (s, p-PPh3), 130.8 (s, p-PPhR2),
[Rh(PPh3)3(Cl)] (0.020 g, 0.021 mmol, 15 mol%), and toluene (10 mL),
flushed with H2, and fitted with a balloon of H2. The mixture was stirred for
24 h. Solvent was removed by oil pump vacuum. The residue was rinsed
through a silica plug with CH2Cl2. Solvent was removed by oil pump
vacuum to give 7 as an orange-red gum (0.162 g, 0.124 mmol, 93%).
1H NMR (300 MHz, CDCl3, 208C): d ˆ 7.46 ± 7.35 (m, 30H, 6Ph), 5.23, 4.62,
4.57, 4.12 (4m, 4 Â 2H, 2C5H4), 2.19 (m, 4H, 2C5H4CH2), 1.50 ± 1.22 (m,
129.3 (d, 3J(C,P) ˆ 11 Hz, m-PPh3), 129.0 (d, 3J(C,P) ˆ 11 Hz, m-PPhR2),
2
2
ˆ
ˆ
128.5 (d, J(C,P) ˆ 8 Hz, CH ), 128.3 (d, J(C,P) ˆ 8 Hz, C'H ), 121.8 (d,
3
3
ˆ
ˆ
J(C,P) ˆ 13 Hz, CH2), 121.7 (d, J(C,P) ˆ 13 Hz, C'H2), 92.7 (s, C5H5),
35.6 (d, 1J(C,P) ˆ 35 Hz, PCH2), 31.4 (d, 1J(C,P) ˆ 35 Hz, PC'H2); 31P{1H}
NMR (161 MHz, CDCl3, 328C): d ˆ 10.3 (d, 2J(P,P) ˆ 10 Hz, PPh3), 19.0
(d, 2J(P,P) ˆ 10 Hz, PPhR2); IR (solid): nÄ ˆ 1702 (NO) cm 1; MS (FAB,
‡
3-NBA): m/z (%): 734 (100) [M] of cation; elemental analysis calcd (%)
3942
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0718-3942 $ 17.50+.50/0
Chem. Eur. J. 2001, 7, No. 18

Olefin Metathesis
3931±3950
1
114.2 (s, CH2), 34.0 (s, CH2CH ), 31.3 (d, J(C,P) ˆ 11 Hz, PCH2),[57] 29.0
ˆ
ˆ
for C36H35F3NO4P2SRe (882.88): C 49.98, H 4.11, N 1.59; found: C 50.10, H
4.21, N 1.49.
(s, 2  intensity, CH2CH2CH2CH CH2), 28.5 (d, 3J(C,P) ˆ 11 Hz,
ˆ
5
‡
PCH2CH2CH2), 26.1 (d, 2J(C,P) ˆ 15 Hz, PCH2CH2); 31P{1H} NMR
(161 MHz, CDCl3, 328C): d ˆ 23.8 (s); MS (FAB, 3-NBA/CH2Cl2): m/z
ˆ
[(h -C5H5)Re(NO)(PPh3)(P(Me)CH2CH CHCH2)]
TfO
(11a):
A
Schlenk flask was charged with 10a (0.204 g, 0.249 mmol) and CH2Cl2
(150 mL). Solid 1 (0.016 g, 0.017 mmol, 8 mol%) was added in four
portions over 1 h with stirring. After another hour, the mixture was filtered
through a silica plug. Solvent was removed from the filtrate by oil pump
vacuum. Column chromatography (silica gel, 10 Â 2 cm, 95:5 v/v CH2Cl2/
methanol) gave a yellow eluate which was dried by oil pump vacuum to
give 11a as a yellow foam (0.193 g, 0.244 mmol, 96%). M.p. 768C; 1H NMR
(400 MHz, CDCl3, 328C, TMS): d ˆ 7.55 ± 7.26 (m, 15H, 3Ph), 5.78 (m, 2H,
‡
(%): 331 (100) [M] ; elemental analysis calcd (%) for C22H35P (330.49): C
79.95, 10.67; found: C 79.95, H 9.90.
5
‡
ˆ
[(h -C5Me5)Re(NO)(PPh((CH2)6CH CH2)2)(CO)] BF4 (14): A Schlenk
flask was charged with [(h5-C5Me5)Re(NO)(NCMe)(CO)] BF4 (0.190 g,
‡
0.374 mmol), 13 (0.103 g, 0.312 mmol), and ClCH2CH2Cl (20 mL), and fitted
with a condenser. The solution was heated under reflux (15 h). Solvent was
removed by oil pump vacuum. Column chromatography (silica gel, 20 Â
2 cm, CH2Cl2) gave a red by-product band. The eluent was changed to 97:3
v/v CH2Cl2/methanol (yellow band containing some 14) and then 92:8 v/v
CH2Cl2/methanol. Solvent was removed from the last series of fractions by
oil pump vacuum to give spectroscopically pure 14 (0.101 g, 0.127 mmol,
41%). An analytical sample was obtained by further column chromatog-
raphy (silica gel, 7:3 v/v CH2Cl2/acetone). 1H NMR (400 MHz, CDCl3,
ˆ
CH CH), 5.56 (s, 5H, C5H5), 2.63 (m, 3H of PCHH' ‡ PC'HH'), 2.17 (m,
1H of PCHH' ‡ PC'HH'), 1.62 (d, 2J(H,P) ˆ 10 Hz, 3H, PCH3); 13C{1H}
NMR (100 MHz, CDCl3, 328C, TMS): d ˆ 133.9 (d, 1J(C,P) ˆ 56 Hz, i-Ph),
133.2 (d, 2J(C,P) ˆ 11 Hz, o-Ph), 131.6 (d, 4J(C,P) ˆ 1 Hz, p-Ph), 129.3 (d,
3
ˆ
ˆ
J(C,P) ˆ 11 Hz, m-Ph), 128.9 (s, CH ), 128.3 (s, C'H ), 91.9 (s, C5H5), 38.8
(d, 1J(C,P) ˆ 35 Hz, PCH2), 35.3 (d, 1J(C,P) ˆ 33 Hz, PC'H2), 17.4 (d,
1J(C,P) ˆ 34 Hz, PCH3); 31P{1H} NMR (161 MHz, CDCl3, 328C): d ˆ 13.8
(d, 2J(P,P) ˆ 14 Hz, PPh3), 15.8 (d, 2J(P,P) ˆ 14 Hz, PMeR2); IR (KBr):
ˆ
328C, TMS): d ˆ 7.56 ± 7.45 (m, 5H, Ph), 5.74 (m, 2H, 2CH ), 4.92 (m, 4H,
ˆ
ˆ
2
CH2), 2.37 (m, 4H, 2PCH2), 2.01 (m, 4H, 2CH2CH ), 1.93 (s, 15H,
nÄ ˆ 1695 (NO) cm 1; MS (FAB, 3-NBA/CH2Cl2): m/z (%): 644 (100) [M]
‡
C5(CH3)5), 1.45 ± 1.25 (m, 16H, 8CH2); 13C{1H} NMR (100 MHz, [D6]ben-
2
of cation; elemental analysis calcd (%) for C29H29F3NO4P2SRe (792.77): C
43.94, H 3.69, N 1.77; found: C 44.33, H 3.97, N 1.46.
ˆ
zene, 328C): d ˆ 203.8 (d, J(C,P) ˆ 8 Hz, ReCO), 139.0 (s, CH ), 131.7 (d,
1J(C,P) ˆ 53 Hz, i-Ph,), 129.9 (d, 2J(C,P) ˆ 11 Hz, o-Ph), 128.6 (d, 3J(C,P) ˆ
5
‡
ˆ
10 Hz, m-Ph), 127.8 (s, p-Ph), 114.5 (s, CH2), 106.1 (s, C5(CH3)5), 34.0 (s,
ˆ
[(h -C5H5)Re(NO)(PPh3)(P(Ph)CH2CH CHCH2)] TfO (11b): Com-
plex 10b (0.100 g, 0.130 mmol), CH2Cl2 (150 mL), and solid 1 (0.006 g,
0.005 mmol, 4 mol% in two portions) were combined in a procedure
analogous to that given for 11a. An identical workup gave 11b as a yellow
foam (0.071 g, 0.083 mmol, 64%). M.p. 808C;[18] 1H NMR (400 MHz,
ˆ
CH2CH ), 30.6 (d, J(C,P) ˆ 8 Hz, CH2), 30.4 (d, J(C,P) ˆ 11 Hz, CH2), 28.9
(s, 2 Â intensity, CH2), 28.8 (s, CH2), 24.0 (s, CH2), 9.7 (s, C5(CH3)5); 31P{1H}
NMR (161 MHz, CDCl3, 328C): d ˆ 0.4 (s); IR (solid film): nÄ ˆ 1984 (CO),
1722 (NO) cm 1; MS (FAB, 3-NBA/CH2Cl2): m/z (%): 710 (100) [M] of
‡
cation; elemental analysis calcd (%) for C33H50BF4NO2PRe (796.75): C
49.75, H 6.33, N 1.76; found: C 49.81, H 6.59, N 1.73.
ˆ
CDCl3, 328C, TMS): d ˆ 7.49 ± 7.02 (m, 20H, 4Ph), 5.74 (m, 2H, CH CH),
5.43 (s, 5H, C5H5), 3.11 ± 2.78 (m, 4H, 2PCH2); 13C{1H} NMR (100 MHz,
CDCl3, 328C, TMS): d ˆ 134.8 (d, 1J(C,P) ˆ 49 Hz, i-PPhR2), 133.7 (d,
1J(C,P) ˆ 56 Hz, i-PPh3), 133.1 (d, 2J(C,P) ˆ 11 Hz, o-PPh3/PPhR2), 131.6
5
ˆ
[(h -C5Me5)Re(NO)(PPh((CH2)6CH CH2)2)(Cl)] (15): A Schlenk flask
was charged with 14 (0.300 g, 0.377 mmol) and THF (20 mL). Then LiAlH4
(0.047 g, 1.243 mmol) was added with stirring. After 2 h, small amounts of
water were added until gas evolution ceased. Solvent was removed by oil
pump vacuum. Then CH2Cl2 (ca. 20 mL) was added, and the sample
filtered. Aqueous HCl (12n; 0.20 mL, 2.4 mmol) was added with stirring.
After 0.5 h, the sample was concentrated and filtered through a silica plug
(3 cm). Solvent was removed from the filtrate by oil pump vacuum to give
15 as dark red solid (152 mg, 0.213 mmol, 56%). M.p. 162 1748C;
1H NMR (400 MHz, CDCl3, 328C, TMS): d ˆ 7.72 ± 7.63 (m, 2H of Ph),
(d, 4J(C,P) ˆ 2 Hz, p-PPh3), 130.8 (s, p-PPhR2), 129.8 (d, 3J(C,P) ˆ 10 Hz,
3
ˆ
m-PPh3), 129.2 (d, J(C,P) ˆ 10 Hz, m-PPhR2), 129.1 (s, CH ), 129.0 (s,
C'H ), 92.5 (s, C5H5), 39.9 (d, 1J(C,P) ˆ 34 Hz, PCH2), 34.6 (d, 1J(C,P) ˆ
ˆ
33 Hz, PC'H2); 31P{1H} NMR (161 MHz, CDCl3, 328C): d ˆ 11.7 (d,
2J(P,P) ˆ 12 Hz, PPh3), 1.4 (d, 2J(P,P) ˆ 12 Hz, PPhR2); IR (solid film):
nÄ ˆ 1695 (NO) cm 1; MS (FAB, 3-NBA): m/z (%): 706 (100) [M] of cation.
‡
PPh2(CH2)6CH CH2 (12):[21] A Schlenk flask was charged with PPh2H
ˆ
(3.210 g, 17.24 mmol) and THF (90 mL). Then nBuLi (2.5m in hexanes;
7.2 mL, 18 mmol) was added dropwise with stirring. The solution turned
orange-red.[20a] After 10 min, a solution of 4 (3.130 g, 16.38 mmol) in THF
(10 mL) was added. The sample turned light yellow. After 3 h, solvent was
removed by oil pump vacuum to give a white solid suspended in an oil.
Hexane (30 mL) was added, and the mixture was passed through a silica
plug (2 cm). Solvent was removed by oil pump vacuum. The residue was
distilled under vacuum to give 12 as a viscous colorless liquid (4.515 g,
15.23 mmol, 88%). Procedures using KPPh2 (Fluka, 0.5m in THF) gave
equivalent results. 1H NMR (300 MHz, CDCl3, 208C): d ˆ 7.45 ± 7.32 (m,
ˆ
7.15 ± 7.00 (m, 3H of Ph), 5.83 ± 5.66 (m, 2H, 2CH ), 5.06 ± 4.92 (m, 4H,
ˆ
ˆ
2
CH2), 2.76 ± 2.38 (m, 4H, 2PCH2), 2.00 ± 1.84 (m, 4H, 2CH2CH ), 1.53
(s, 15H, C5(CH3)5), 1.37 ± 1.00 (m, 16H, 8CH2); 13C{1H} NMR (100 MHz,
2
ˆ
CDCl3, 328C, TMS): d ˆ 139.0 (s, CH ), 131.7 (d, J(C,P) ˆ 12 Hz, o-Ph),
131.1 (partially obscuredd, 1J(C,P) ˆ 50 ± 56 Hz, i-Ph), 129.7 (s, p-Ph), 128.7
3
ˆ
(d, J(C,P) ˆ 11 Hz, m-Ph), 114.6 (s, CH2), 99.4 (s, C5(CH3)5), 34.0 (s,
ˆ
CH2CH ), 31.3 (d, J(C,P) ˆ 13 Hz, CH2), 29.1 (d, J(C,P) ˆ 9 Hz, CH2), 28.8
(s, CH2), 26.3 (s, CH2), 23.2 (s, CH2), 10.1 (s, C5(CH3)5); 31P{1H} NMR
(161 MHz, CDCl3, 328C): d ˆ 6.9 (s); IR (solid film): nÄ ˆ 1637
(NO) cm 1; MS (FAB, 3-NBA): m/z (%): 717 (100) [M] ; elemental
‡
ˆ
ˆ
10H, 2Ph), 5.79 (m, 1H, CH ), 5.02 ± 4.91 (m, 2H, CH2), 2.07 ± 1.99 (m,
4H, CH2CH ‡ PCH2), 1.45 ± 1.27 (m, 8H, 4CH2); 13C{1H} NMR (75 MHz,
ˆ
analysis calcd (%) for C32H50ClNOPRe (717.38): C 53.58, H 7.02, N 1.95;
found: C 53.40, H 6.81, N 1.59.
1
ˆ
CDCl3, 208C): d ˆ 139.3 (s, CH ), 139.2 (d, J(C,P) ˆ 16 Hz, i-Ph), 132.9 (d,
2J(C,P) ˆ 19 Hz, o-Ph), 128.6 (d, 3J(C,P) ˆ 9 Hz, m-Ph), 128.6 (s, p-Ph),
5
‡
ˆ
[(h -C5Me5)Re(NO)(P(Ph)(CH2)6CH CH(CH2)6)(CO)] BF4 (16):
A
114.4 (s, CH2), 34.0 (s, CH2CH ), 31.3 (d, J(C,P) ˆ 13 Hz, PCH2),[57] 29.0
1
ˆ
ˆ
Schlenk flask was charged with 14 (0.150 g, 0.188 mmol), CH2Cl2
(150 mL) and 1 (0.0064 g, 0.0078 mmol, 4 mol%). The sample was stirred
for 14 h, and filtered through a Celite plug (2 cm). Solvent was removed by
oil pump vacuum to give 16 as a dark solid of >98% spectroscopic purity
(0.142 g, 0.178 mmol, 94%; Z/E (tentative)[23] 44:56[55b,c]). Extensive
attempts to obtain analytically pure samples were unsuccessful. M.p.
688C;[18] 1H NMR (400 MHz, CDCl3, 328C, TMS): d ˆ 7.56 ± 7.45 (m, 5H,
(s, 2  intensity, CH2CH2CH2CH CH2), 28.2 (d, 3J(C,P) ˆ 11 Hz,
ˆ
PCH2CH2CH2), 26.1 (d, 2J(C,P) ˆ 16 Hz, PCH2CH2); 31P{1H} NMR
(161 MHz, CDCl3, 328C): d ˆ 15.8 (s); elemental analysis calcd (%) for
C20H25P (296.39): C 81.05, 8.50; found: C 81.02, H 8.44.
PPh((CH2)6CH CH2)2 (13):[21] A Schlenk flask was charged with PPhH2
ˆ
(0.938 g, 8.52 mmol) and THF (40 mL) and was cooled to 08C. Then nBuLi
(1.8m in hexanes, 10.1 mL, 18 mmol) was added dropwise with stirring over
10 min.[20b] After another 10 min, a solution of 4 (3.260 g, 17.06 mmol) in
THF (5 mL) was added. The cold bath was removed. After 2 h, solvent was
removed by oil pump vacuum. The residue was filtered through a silica plug
(3 cm) with hexane (3 Â 20 mL). The filtrate was taken to dryness by oil
pump vacuum. The residue was distilled (10 2 bar, 111 ± 1158C) to give 13
ˆ
Ph), 5.42 ± 5.38/5.36 ± 5.26 (2m, 2H, E/Z CH CH, 56:44), 2.43 (m, 4H,
ˆ
2PCH2), 2.10 (m, 4H, 2CH2CH ), 1.97/1.96 (2s, 15H, C5(CH3)5), 1.50 ± 1.21
(m, 16H, 8CH2); 13C{1H} NMR (100 MHz, CDCl3, 328C, TMS): d ˆ 203.7
ˆ
(brs, ReCO) 137.3/137.0 (2s, CH ), 134.7 ± 126.8 (PPh signals), 99.1/99.0
ˆ
(2s, C5(CH3)5), 36.0/35.4 (2s, CH2CH ), 32.9 ± 21.9 (CH2 signals), 10.1/10.0
(2s, C5(CH3)5); 31P{1H} NMR (161 MHz, CDCl3, 328C): d ˆ 0.71/ 0.85
(2s, Z/E, 44:56); IR (solid film): nÄ ˆ 1980 (CO), 1718 (NO) cm 1; MS (FAB,
as
a
viscous colorless liquid (2.200 g, 6.657 mmol, 78%). 1H NMR
‡
(400 MHz, CDCl3, 328C): d ˆ 7.63 (m, 1H of Ph), 7.49 (m, 2H of Ph),
3-NBA/CH2Cl2): m/z (%): 682 (100) [M] of cation.
ˆ
ˆ
7.34 (m, 2H of Ph), 5.79 (m, 2H, 2CH ), 4.90 (m, 4H, 2 CH2), 1.98 (m, 4H,
5
ˆ
[(h -C5Me5)Re(NO)(P(Ph)(CH2)6CH CH(CH2)6)(Cl)] (17)
2CH2CH ), 1.69 (m, 4H, 2PCH2), 1.42 ± 1.08 (m, 16H, 8CH2); 13C{1H}
ˆ
ˆ
NMR (100 MHz, CDCl3, 328C): d ˆ 139.4 (m, i-Ph), 139.1 (s, CH ), 132.6
A: A Schlenk flask was charged with 15 (0.074 g, 0.105 mmol), 1 (0.0042 g,
0.0051 mmol, 5 mol%), and CH2Cl2 (150 mL). The sample was stirred for
(d, 2J(C,P) ˆ 18 Hz, o-Ph), 128.2 (d, 3J(C,P) ˆ 20 Hz, m-Ph), 128.4 (s, p-Ph),
Chem. Eur. J. 2001, 7, No. 18
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0718-3943 $ 17.50+.50/0
3943

J. Gladysz et al.
FULL PAPER
12 h, concentrated by oil pump vacuum to ca. 5 mL, and filtered through a
silica plug (3 cm). Solvent was removed by oil pump vacuum to give 17 as a
dark red solid (0.065 g, 0.094 mmol, 89%).
13C{1H} NMR (75 MHz, CDCl3, 208C, E isomer unless noted): d ˆ 190.0,
2
ˆ
189.3 (2t, 1:2, J(C,P) ˆ 28 Hz, ReCO), 131.1 (CH CH), 134 ± 133 (com-
plex, i-Ph), 133.2, 132.8 (2virtual t, J(C,P) ˆ 5 Hz,[59] o-Ph), 130.1, 130.1 (2s,
ˆ
p-Ph), 128.7, 128.3 (2virtual t, J(C,P) ˆ 4 Hz, m-Ph), 32.3 (s, CH2CH (E)),
B: Complex 16 (0.160 g, 0.208 mmol), THF (10 mL), LiAlH4 (0.028 g,
0.735 mmol), CH2Cl2 (ca. 20 mL),[25] and aqueous HCl (12n, 0.10 mL,
1.2 mmol) were combined in a procedure analogous to that given for 15. An
identical workup gave 17 as dark red solid (0.110 g, 0.160 mmol, 76%; Z/E
(tentative, range for both syntheses)[23] 41 ± 43:59 ± 57[55b,c]). M.p. 165 ±
1728C; 1H NMR (400 MHz, CDCl3, 328C, TMS): d ˆ 7.60 ± 7.26 (m, 5H,
ˆ
30.5 (virtual t, J(C,P) ˆ 6 Hz, CH2), 29.5 (s, CH2CH (Z)) 29.2 (s, CH2, Z at
28.0), 28.7 (s, CH2, Z at 27.0), 25.5 (virtual t, J(C,P) ˆ 12 Hz, CH2), 24.4
(br s, CH2); 31P{1H} NMR (121 MHz, CDCl3, 208C): d ˆ -8.2 (s); IR
(CDCl3/Nujol): nÄ ˆ 2033/2031, 1950/1952, 1904/1900 (CO) cm 1; MS (FAB,
‡
‡
3-NBA/CH2Cl2): m/z (%): 914 (17) [M] , 886 (70) [M CO] , 858 (42)
‡
‡
‡
[M 2CO] , 835 (100) [M Br] , 807 (25) [M Br CO] ; elemental
analysis calcd (%) for C41H46BrO3P2Re (914.87): C 53.83, 5.07; found: C
53.81, H 5.10.
ˆ
Ph), 5.34 ± 5.30/5.29 ± 5.21 (2m, 2H, E/Z CH CH, 59:41), 2.65 ± 2.10 (m,
ˆ
4H, 2PCH2), 2.05 ± 1.81 (m, 4H, 2CH2CH ), 1.56/1.55 (2s, 15H, C5(CH3)5),
1.51 ± 1.18 (m, 16H, 8CH2); 13C{1H} NMR (100 MHz, CDCl3, 328C, TMS):
d ˆ 131.3 (2overlapping d, i-Ph), 131.24/131.15 (CH ), 131.1 (d, 2J(C,P) ˆ
ˆ
fac-[(CO)3Re(Br)(P(Ph)2(CH2)14P(Ph)2)] (23):
A Schlenk flask was
14 Hz, o-Ph), 129.6 (d, 3J(C,P) ˆ 16 Hz, m-Ph), 128.0 (s, p-Ph), 99.4 (s,
charged with 22 (0.035 g, 0.038 mmol), 10% Pd/C (0.004 g, 0.004 mmol),
and toluene/ethanol (20 mL, 1:1 v/v), flushed with H2, and fitted with a
balloon of H2. The suspension was stirred overnight. Solvent was removed
by oil pump vacuum. The residue was extracted with CH2Cl2. Column
chromatography (silica gel, CH2Cl2) gave a product band which was taken
to dryness by rotary evaporation to give 23 as a white powder (0.034 g,
ˆ
C5(CH3)5), 32.4/31.9 (2s, CH2CH ), 29.7 ± 24.0 (CH2 signals), 9.9/9.8 (2s,
C5(CH3)5); 31P{1H} NMR (161 MHz, CDCl3, 328C): d ˆ 8.42/ 8.81 (2s,
Z/E, 43:57); IR (solid film): nÄ ˆ 1637 (NO) cm 1; MS (FAB, 3-NBA/
‡
CH2Cl2): m/z (%): 689 (100) [M] ; elemental analysis calcd (%) for
C30H46ClNOPRe (689.33): C 52.27, H 6.73, N 2.03; found: C 52.17, H 7.05, N
1.90.
1
0.037 mmol, 98%). M.p. 186 ± 1888C; H NMR (300 MHz, CDCl3, 208C):
[(h5-C5Me5)Re(NO)(P(Ph)(CH2)14)(Cl)] (18): A Fischer± Porter bottle
was charged with 17 (0.075 g, 0.108 mmol), freshly degassed ethanol/
toluene (30 mL, 1:1 v/v), and [Rh(PPh3)3(Cl)] (0.0074 g, 0.005 mmol,
7 mol%). The mixture was stirred under H2 (60 psig, 36 h). Solvent was
removed by oil pump vacuum, and CH2Cl2 (12 mL) was added. The sample
was filtered through a silica plug (2 cm) and concentrated to about 1 mL.
Hexane was added, and solvent was removed by oil pump vacuum to give
18 as a red powder (0.053 g, 0.077 mmol, 72%). M.p. 180 ± 1828C (DSC,
183.68C); 1H NMR (400 MHz, CDCl3, 328C, TMS): d ˆ 7.61 ± 7.24 (m, 5H,
Ph), 2.49 ± 2.02 (m, 4H, 2PCH2), 1.61 (s, 15H, C5(CH3)5), 1.51 ± 1.16 (m,
24H, 12CH2); 13C{1H} NMR (100 MHz, CDCl3, 328C, TMS): d ˆ 134.2 (d,
2J(C,P) ˆ 10 Hz, o-Ph), 131.2 (d, 3J(C,P) ˆ 23 Hz, m-Ph), 130.3 (m, i-Ph),
128.1 (s, p-Ph), 99.4 (s, C5(CH3)5), 29.7 ± 22.0 (unresolved and diastereo-
topic CH2 signals), 9.9 (s, C5(CH3)5); 31P{1H} NMR (161 MHz, CDCl3,
328C): d ˆ 8.35 (s); IR (solid film): nÄ ˆ 1640 (NO) cm 1; MS (FAB,
d ˆ 7.67 ± 7.22 (m, 20H, 4Ph), 2.87 ± 2.83 (m, 2H, 2'), 2.13 ± 2.06 (m, 2H,
2PCHH'), 1.38 ± 1.19 (m, 24H, 12CH2); 13C{1H} NMR (75 MHz, CDCl3,
208C): d ˆ 190.1, 189.6 (2t, 1:2, 2J(C,P) ˆ 28.7, ReCO), 134 ± 133 (complex,
i-Ph), 133.3, 132.7 (2virtual t, J(C,P) ˆ 5 Hz,[59] o-Ph), 130.2, 130.1 (2s, p-
Ph), 128.7, 128.3 (2virtual t, J(C,P) ˆ 5 Hz, m-Ph), 30.5 (virtual t, J(C,P) ˆ
6 Hz, CH2), 27.82 (s, CH2), 27.79 (s, CH2), 27.5 (s, CH2), 26.8 (s, CH2), 25.9
(virtual t, J(C,P) ˆ 12 Hz, CH2), 23.8 (brs, CH2); 31P{1H} NMR (121 MHz,
CDCl3, 208C): d ˆ 8.2 (s); IR (CDCl3/Nujol): nÄ ˆ 2032/2036, 1951/1958,
‡
1904/1903 (CO) cm 1; MS (FAB, 3-NBA/CH2Cl2): m/z (%): 916 (13) [M] ,
‡
‡
‡
888 (96) [M CO] , 860 (79) [M 2CO] , 837 (100) [M Br] , 809 (53)
‡
[M Br CO] ; elemental analysis calcd (%) for C41H48BrO3P2Re
(916.88): C 53.71, 5.28; found: C 53.76, H 5.30.
ˆ
cis-[(Cl)2Pt(PPh2(CH2)6CH CH2)2] (24): A Schlenk flask was charged
with [(Cl)2Pt(COD)] (0.160 g, 0.432 mmol)[60] and CH2Cl2 (10 mL). A
solution of 12 (0.260 g, 0.877 mmol) in CH2Cl2 (5 mL) was added via
cannula with stirring. After 5 h, the mixture was filtered through a Celite
plug (3 cm). Solvent was removed by oil pump vacuum. The oily residue
was washed with hexane (3 Â 5 mL). Column chromatography (alumina,
benzene) gave a product band which was taken to dryness by oil pump
vacuum to give 24 as a white powder (0.257 g, 0.299 mmol, 70%). M.p. 98 ±
‡
‡
3-NBA): m/z (%): 691 (100) [M] , 386 (90) [M (PPh(CH2)14)] ;
elemental analysis calcd (%) for C30H48ClNOPRe (691.35): C 52.12, H
7.00, N 2.03; found: C 52.17, H 7.05, N 1.90.
ˆ
fac-[(CO)3Re(Br)(PPh2(CH2)6CH CH2)2] (21):
A Schlenk flask was
charged with 12 (0.750 g, 2.530 mmol), CHCl3 (20 mL), and [(CO)5Re(Br)]
(0.514 g, 1.266 mmol),[58] and fitted with a condenser. The mixture was
heated under reflux (56 h; monitored by IR). Solvent was removed by
rotary evaporation. Column chromatography (silica gel, 1:1 v/v CH2Cl2/
hexane) gave a product band which was taken to dryness by rotary
evaporation. The colorless oil solidified over the course of one week, and
was dried by oil pump vacuum to give 21 as a white powder (0.863 g,
1
1008C; H NMR (300 MHz, CDCl3, 208C): d ˆ 7.51 ± 7.22 (m, 20H, 4Ph),
ˆ
ˆ
5.75 (m, 2H, 2CH ), 4.99 ± 4.89 (m, 4H, 2 CH2), 2.30 ± 2.10 (m, 4H,
ˆ
2PCH2), 1.99 ± 1.92 (m, 4H, 2CH2CH ), 1.60 ± 1.45 (m, 4H, 2PCH2CH2),
1.27 ± 1.15 (m, 12H, 6CH2); 13C{1H} NMR (75 MHz, CDCl3, 208C): d ˆ
ˆ
139.1 (CH ), 133.6 (virtual t, J(C,P) ˆ 5 Hz, o-Ph), 131.0 (s, p-Ph), 129.8 (d,
1J(C,P) ˆ 64 Hz, i-Ph), 128.4 (virtual t, J(C,P) ˆ 5 Hz, m-Ph), 114.5 (s,
1
ˆ
ˆ
CH2), 33.8 (s, CH2CH ), 30.8 (virtual t, J(C,P) ˆ 8 Hz, CH2), 28.8 (2s,
2CH2), 28.6 (brs, CH2), 25.2 (s, CH2); 31P{1H} NMR (121 MHz, CDCl3,
208C): d ˆ 7.6 (s, 1J(P,Pt) ˆ 3652 Hz);[61] MS (FAB, 3-NBA/CH2Cl2): m/z
0.915 mmol, 72%). M.p. 101 ± 1028C; H NMR (300 MHz, CDCl3, 208C):
ˆ
d ˆ 7.44 ± 7.34 (m, 20H, 4Ph), 5.76 (m, 2H, 2CH ), 4.99 ± 4.90 (m, 4H,
ˆ
ˆ
2
CH2), 2.56 (m, 2H, 2PCHH'), 2.00± 1.88 (m, 6H, 2CH2CH ‡ 2PCHH'),
‡
‡
1.59 ± 0.89 (m, 16H, 8CH2); 13C{1H} NMR (75 MHz, CDCl3, 208C): d ˆ
(%): 858 (2) [M] , 823 (100) [M Cl] , 489 (80) [M 2Cl
‡
2
ˆ
ˆ
Ph2P(CH2)6CH CH2] ; elemental analysis calcd (%) for C40H50Cl2P2Pt
(858.77): C 55.94, 5.87; found: C 55.77, H 5.82.
190.2, 189.5 (2t, 1:2, J(C,P) ˆ 25 Hz, ReCO), 139.2 (CH ), 134 ± 132
(complex, i-Ph), 133.3, 133.0 (2virtual t, J(C,P) ˆ 5 Hz,[59] o-Ph), 130.2 (s, p-
ˆ
ˆ
Ph), 128.5 (m, m-Ph), 114.5 (s, CH2), 33.8 (s, CH2CH ), 30.9 (virtual t,
J(C,P) ˆ 6 Hz, CH2), 28.9 (s, CH2), 28.7 (s, CH2), 26.5 (virtual t, J(C,P) ˆ
14 Hz, CH2), 24.1 (brs, CH2); 31P{1H} NMR (121 MHz, CDCl3, 208C): d ˆ
8.4 (s); IR (CDCl3/Nujol): nÄ ˆ 2035/2029, 1952/1948, 1906/1906 (CO)
ˆ
cis-[(Cl)2Pt(P(Ph)2(CH2)6CH CH(CH2)6P(Ph)2)] (25): A Schlenk flask
was charged with 24 (0.257 g, 0.299 mmol) and CH2Cl2 (110 mL). Another
Schlenk flask was charged with 1 (0.005 g, 0.006 mmol, 2 mol%) and
CH2Cl2 (10 mL). The latter solution was added by cannula to the former
with stirring. The mixture was heated under reflux (3 h), concentrated to
about 3 mL, and purified by chromatography on a short silica gel column
(CH2Cl2). Solvent was removed by oil pump vacuum to give 25 as a white
powder (0.177 g, 0.213 mmol, 71%; Z/E <2: > 98[54, 55a]). M.p. 246 ± 2488C;
1H NMR (300 MHz, CDCl3, 208C): d ˆ 7.44 ± 7.20 (m, 20H, 4Ph), 5.44 (m,
cm 1; MS (FAB, 3-NBA/CH2Cl2): m/z (%): 942 (8) [M] , 914 (50) [M
‡
‡
‡
‡
CO] , 886 (28) [M 2CO] , 863 (100) [M Br] , 835 (43) [M Br
‡
CO] ; elemental analysis calcd (%) for C43H50BrO3P2Re (942.92): C
54.77, 5.34; found: C 54.62, H 5.36.
ˆ
fac-[(CO)3Re(Br)(P(Ph)2(CH2)6CH CH(CH2)6P(Ph)2)] (22): A Schlenk
ˆ
ˆ
flask was charged with 21 (0.286 g, 0.303 mmol) and CH2Cl2 (110 mL).
Another Schlenk flask was charged with 1 (0.005 g, 0.006 mmol; 2 mol%)
and CH2Cl2 (10 mL). The latter solution was added by cannula to the
former with stirring. The mixture was heated under reflux (3 h). Solvent
was removed by rotary evaporation. Column chromatography (silica gel,
CH2Cl2) gave a product band which was taken to dryness by rotary
evaporation to give 22 as a white powder (0.221 g, 0.242 mmol, 80%; Z/E
17 ± 20:83 ± 80[54, 55a]). M.p. 184 ± 1858C; 1H NMR (300 MHz, CDCl3, 208C):
2H, CH CH), 2.16 ± 2.06 (m, 8H, 2PCH2‡2CH2CH ), 2.03 ± 1.92, 1.60 ±
1.35 (2m, 16H, 8CH2); 13C{1H} NMR (75 MHz, CDCl3, 208C): d ˆ 133.3
(virtual t, J(C,P) ˆ 5 Hz, o-Ph), 133.6 ± 133.1 (complex, i-Ph), 131.5
ˆ
(CH CH), 130.9 (s, p-Ph), 128.3 (virtual t, J(C,P) ˆ 5 Hz, m-Ph), 32.2 (s,
ˆ
CH2CH (E)), 30.6 (virtual t, J(C,P) ˆ 9 Hz, CH2), 29.3 (virtual t, J(C,P) ˆ
10 Hz, CH2), 29.1 (s, CH2), 28.4 (s, CH2), 27.3 (brs, CH2); 31P{1H} NMR
(121 MHz, CDCl3, 208C): d ˆ 7.9 (s, 9 %, 1J(P,Pt) ˆ 3631 Hz,[61] assigned to
dimeric compound 26 as described in the text), 7.7 (s, 91%, 1J(P,Pt) ˆ
d ˆ 7.62 ± 7.23 (m, 20H, 4Ph), 5.39 (m, 2H, CH CH), 2.77 (m, 2H,
3627 Hz);[61] MS (FAB, 3-NBA/CH2Cl2): m/z (%): 1625 (46) [M Cl] for
‡
ˆ
‡
ˆ
2PCHH'), 2.07 (m, 6H, 2PCHH'‡2CH2CH ), 1.56 ± 1.18 (m, 16H, 8CH2);
26, 795 (63) [M Cl] for 25, 757 (100); osmometry (CHCl3): calcd for 25
3944
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0718-3944 $ 17.50+.50/0
Chem. Eur. J. 2001, 7, No. 18

Olefin Metathesis
3931±3950
ˆ
830.8; found 844; elemental analysis calcd (%) for C38H46Cl2P2Pt (830.71):
C 54.94, 5.58; found: C 54.91, H 5.57.
CH2CH ), 30.0 (s, C(CH3)3), 29.6 (s, SCH2), 28.7 (s, 2 Â intensity, CH2), 28.6
‡
(s, CH2), 27.2 (s, CH2); MS (FAB, 3-NBA/CH2Cl2): m/z (%): 666 (12) [M] ,
‡
‡
631 (22) [M Cl] , 394 (50) [M 2Cl RSR'] , 394 (93) [M 2Cl
RSR' C(CH3)3] , 57 (100) [C(CH3)3] ; elemental analysis calcd (%) for
C24H48Cl2S2Pt (666.76): C 43.23, H 7.26; found: C 43.21, H 7.32.
ˆ
S(Et)(CH2)6CH CH2 (27): A flask was charged with NaOH (0.600 g,
‡
‡
15.0 mmol), water (ca. 4 mL, to give a solution), ethanol (15 mL), and
HSEt (0.930 g, 15.0 mmol), fitted with a condenser, and cooled in an ice
bath. A solution of 4 (2.850 g, 14.91 mmol) in ethanol (5 mL) was added
with stirring over 20 min. The suspension was heated under reflux (4 h) and
stirred at room temperature (12 h). Water (5 mL) and ether (15 mL) were
added. The phases were separated, and the aqueous phase extracted with
ether (2 Â 10 mL). The combined organic phases were dried (Na2SO4).
Solvent was removed by rotary evaporation and the residue vacuum
[31]
ˆ
cis-[(Cl)2Pt(S(Et)(CH2)6CH CH(CH2)6S(Et))] (31):
A Schlenk flask
was charged with 29 (0.200 g, 0.327 mmol) and CH2Cl2 (200 mL) and fitted
with a condenser. The solution was heated under reflux, and a solution of 1
(0.006 g, 0.007 mmol, 2 mol%) in CH2Cl2 (200 mL) was added. After 2 h,
the sample was concentrated to 5 mL and filtered through a silica plug
(3 cm). A small amount of silica was added to the filtrate. Solvent was
removed by oil pump vacuum and the yellow powder added to the top of a
dry silica column. The column was rinsed with hexane/THF (gradient: start,
90:10 v/v; end, 60:40 v/v). Two yellow bands were collected and dried by oil
pump vacuum, giving 31 (faster moving; 0.104 g, 0.179 mmol, 55%; Z/E
21:79[54, 55a]) and 32 (0.045 g, 0.039 mmol, 24%)[18] as yellow gums.
distilled (48 ± 518C) to give 27 as a colorless liquid (2.270 g, 13.17 mmol,
1
ˆ
88%). H NMR (300 MHz, CDCl3, 208C): d ˆ 5.79 (m, 1H, CH ), 4.92 (m,
2H, CH2), 2.51 (q, 3J(H,H) ˆ 7.5 Hz, 2H, SCH2CH3), 2.50 (t, 3J(H,H) ˆ
ˆ
ˆ
8.1 Hz, 2H, SCH2CH2), 2.02 (m, 2H, CH2CH ), 1.57 (m, 2H, CH2), 1.34 (m,
6H, 3CH2), 1.23 (t, 3J(H,H) ˆ 7.5 Hz, 3H, CH3); 13C{1H} NMR (75 MHz,
ˆ
ˆ
ˆ
CDCl3, 208C): d ˆ 138.9 (s, CH ), 114.2 (s, CH2), 33.6 (s, CH2CH ), 31.6
1
ˆ
Data for 31: H NMR (300 MHz, CDCl3, 208C): d ˆ 5.34 (m, 2H, CH CH),
(s, SCH2), 29.5 (s, SC'H2), 28.7 (s, 2 Â intensity, CH2), 28.6 (s, CH2), 25.8 (s,
3.24 (m, 2H, 2SCHH'), 3.05 ± 2.40 (brm, 6H, remaining SCHH'), 1.94 (m,
‡
CH2), 14.7 (s, CH3); MS (80 eV, EI): m/z (%): 172 (25) [M] , 143 (100),
ˆ
4H, 2CH2CH ), 1.82 (m, 4H, 2SCH2CH2), 1.55 ± 1.33 (m, 18H,
‡
[M CH2CH3] ; elemental analysis calcd (%) for C10H20S (172.33): C
6CH2‡2CH3); 13C{1H} NMR (75 MHz, CDCl3, 208C, syn/anti isomers
69.70, H 11.70; found: C 69.72, H 11.58.
ˆ
not assigned): d ˆ 130.4, 130.2, 130.1 (3s, CH CH), 37.5, 35.7 (2s, SCH2),
ˆ
S(tBu)(CH2)6CH CH2 (28): A flask was charged with NaS-tBu (0.920 g,
ˆ
ˆ
32.1 (s, CH2CH (E)), 30.6, 30.2 (2s, CH2), 29.3 (s, CH2CH (Z, tentative)),
28.6, 28.5 (2s, CH2), 27.5, 27.1 (2s, CH2), 12.7 (s, CH3); MS (FAB, 3-NBA/
8.20 mmol) and DMF (20 mL) and cooled to 08C. A solution of 4 (1.110 g,
5.808 mmol) in DMF (5 mL) was added with stirring over 20 min. The
mixture was heated to 1008C (1 h) and cooled to room temperature. Water
(15 mL) was added with stirring. The phases were separated, and the
aqueous phase extracted with ether (3 Â 15 mL). The combined organic
phases were washed with water (5 Â 10 mL) and dried (Na2SO4). Solvent
was removed by rotary evaporator and the oil vacuum distilled (79 ± 828C)
to give 28 as a colorless liquid (0.812 g, 4.05 mmol, 70%). 1H NMR
‡
‡
‡
CH2Cl2): m/z (%): 582 (13) [M] , 547 (19) [M Cl] , 509 (18) [M 2Cl] ,
‡
‡
480 (14) [M 2Cl CH2CH3] , 447 (22) [M 2Cl SCH2CH3] ; elemen-
tal analysis calcd (%) for C18H36Cl2S2Pt (582.52): C 37.11, H 6.23; found: C
37.41, H 6.28.
Data for 32: 1H NMR (300 MHz, CDCl3, 208C): d ˆ 5.29 (m, 4H,
ˆ
2CH CH), 3.21 (m, 4H, 2SCHH'), 3.05 ± 2.40 (brm, 12H, remaining
ˆ
SCHH'), 1.95 (m, 8H, 4CH2CH ), 1.83 (m, 8H, 4SCH2CH2), 1.66 ± 1.33 (m,
ˆ
ˆ
(300 MHz, CDCl3, 208C): d ˆ 5.78 (m, 1H, CH ), 4.94 (m, 2H, CH2), 2.49
36H, 12CH2‡4CH3); 13C{1H} NMR (75 MHz, CDCl3, 208C, syn/anti
isomers present but unassigned): d ˆ 130.3, 130.2, 130.0, 129.8, 129.7, 129.5
3
ˆ
(t, J(H,H) ˆ 7.5 Hz, 2H, SCH2), 2.02 (m, 2H, CH2CH ), 1.53 (m, 2H,
CH2), 1.37 (m, 6H, 3CH2), 1.30 (s, 9H, C(CH3)3); 13C{1H} NMR (75 MHz,
ˆ
ˆ
(6s, CH CH), 37.5, 35.7, 34.1 (3s, SCH2), 32.4, 32.1 (2s, CH2CH (E)), 30.6,
ˆ
ˆ
CDCl3, 208C): d ˆ 139.0 (s, CH ), 114.2 (s, CH2), 41.8 (s, C(CH3)3), 33.7 (s,
ˆ
30.2 (2s, CH2), 29.4, 29.3 (2s, CH2CH (Z, tentative)), 28.6 (s, 2 Â intensity,
ˆ
CH2CH ), 31.0 (s, C(CH3)3), 29.8 (s, CH2), 29.1 (s, CH2), 28.8 (s, 2 Â in-
CH2), 28.5, 27.6, 27.5, 27.0 (4s, CH2), 12.8 (s, 2 Â intensity, CH3); MS (FAB,
‡
tensity, CH2), 28.3 (s, CH2); MS (80 eV, EI): m/z (%): 200 (11) [M] , 185
‡
3-NBA/CH2Cl2): m/z (%): 1128 (10) [M Cl] .
‡
‡
‡
(19) [M CH3] , 143 (47) [M C(CH3)3] , 57 (100) [C(CH3)3] ; elemental
analysis calcd for C12H24S (200.38): C 71.93, H 12.07; found: C 71.94, H
12.24.
[31]
ˆ
cis-[(Cl)2Pt(S(tBu)(CH2)6CH CH(CH2)6S(tBu))] (33): A Schlenk flask
was charged with 30 (0.154 g, 0.231 mmol) and CH2Cl2 (200 mL) and fitted
with a condenser. The solution was heated under reflux, and a solution of 1
(0.005 g, 0.006 mmol, 2 mol%) in CH2Cl2 (5 mL) was added. After 2 h, the
sample was concentrated to 3 mL and filtered through a silica plug (3 mL).
Column chromatography (silica gel, CH2Cl2) gave a yellow band which was
dried by oil pump vacuum to give 33 as a yellow gum (0.106 g, 0.166 mmol,
72%; Z/E 16:84[54, 55a]).[18] 1H NMR (300 MHz, CDCl3, 208C): d ˆ 5.30 (m,
[31]
ˆ
cis-[(Cl)2Pt(S(Et)(CH2)6CH CH2)2] (29): A flask was charged with 27
(0.364 g, 2.11 mmol), methanol (3 mL), and a solution of K2[PtCl4] (0.385 g,
0.928 mmol) in water (5 mL). The mixture was stirred (14 h), and a yellow-
brown oil separated. Solvent was removed by rotary evaporation. The
residue was washed with ethanol (2 Â 5 mL), dried by oil pump vacuum,
dissolved in CH2Cl2 (2 mL), and added to a small amount of silica. Solvent
was removed by oil pump vacuum, and the yellow powder added to the top
of a dry silica column. The column was rinsed with hexane and hexane/THF
(gradient ending at 60:40 v/v). A yellow band was dried by oil pump
vacuum to give 29 as a yellow oil (0.479 g, 0.784 mmol, 84%). 1H NMR
ˆ
2H, CH CH), 3.38 (brm, 2H, 2SCHH'), 2.05 ± 1.98 (m, 6H,
ˆ
2SCHH'‡2CH2CH ), 1.54 (s, 18H, 2C(CH3)3), 1.32 (m, 16H, 8CH2);
13
1
ˆ
C{ H} NMR (100 MHz, CDCl3, 308C): d ˆ 130.3 (s, CH CH), 51.5 (s,
ˆ
C(CH3)3), 32.5 (s, CH2CH (E)), 30.3 (s, SCH2), 30.1 (s, C(CH3)3), 29.6 (s,
ˆ
CH2CH (Z, tentative)), 29.4 (s, CH2), 28.8 (s, CH2), 28.7 (s, CH2), 27.3 (s,
ˆ
ˆ
(300 MHz, CDCl3, 308C): d ˆ 5.76 (m, 2H, 2CH ), 4.97 (m, 4H, 2 CH2),
‡
CH2); MS (80 eV, EI): m/z (%): 638 (3) [M] , 508 (4) [M 2Cl
3.24/3.10 ± 2.40 (2m, 2H ‡ 6H, 2SCHH'R ‡ 2SCHH'R'), 2.02 (m, 4H,
‡
‡
C(CH3)3] , 452 (5) [M 2Cl 2C(CH3)3] , 420 (3) [M 2Cl
ˆ
2CH2CH ), 1.83 (m, 4H, 2SCH2CH2), 1.55 ± 1.33 (m, 18H, 6CH2 ‡ 2CH3);
‡
‡
13C{1H} NMR (75 MHz, CDCl3, 208C, syn/anti isomers): d ˆ 138.9/138.7
SC(CH3)3 C(CH3)3] , 315 (14) [M PtCl2 C(CH3)3] , 259 (38) [M
PtCl2 2C(CH3)3] , 57 (100) [C(CH3)3] .
‡
‡
ˆ
ˆ
(2s, CH ), 114.5/114.4 (2s, CH2), 37.6 (brs, SCH2), 35.7 (brs, SC'H2),
ˆ
33.61/33.57 (2s, CH2CH ), 30.6 (s, 2 Â intensity, CH2), 28.6/28.5 (2s, 1 and
ˆ
trans-[(Cl)(CO)Rh(PPh2(CH2)6CH CH2)2] (34):
A Schlenk tube was
2 Â intensity, CH2), 27.6/27.5 (2s, CH2), 12.76/12.72 (2s, CH3); MS (FAB,
charged with 12 (1.000 g, 3.37 mmol), CH2Cl2 (13 mL), hexane (13 mL),
and [Rh(m-Cl)(COD)]2 (0.415 g, 0.842 mmol).[62] Then CO was bubbled
through the deep orange solution (50 min; volatilized solvent periodically
replaced; color change to deep yellow). Solvent was removed by oil pump
vacuum. Column chromatography (silica gel, 7 Â 2.5 cm, CH2Cl2) gave a
yellow band which was dried by rotary evaporation. Pentane (4 mL) was
added, and the sample kept at 248C. After 2 d, a yellow powder was
collected by filtration and dried by oil pump vacuum to give 34 (1.008 g,
1.33 mmol, 79%). M.p. 64 ± 668C; 1H NMR (400 MHz, CDCl3, 328C,
TMS): d ˆ 7.73 ± 7.68 (m, 8H of 4Ph), 7.38 ± 7.34 (m, 12H of 4Ph), 5.82 ± 5.72
‡
‡
glycerol/2-NPOE/CH2Cl2): m/z (%): 611 (6) [M‡H] , 575 (12) [M Cl] ,
‡
353 (36) [M 2Cl RSR'] ; elemental analysis calcd (%) for
C20H40Cl2S2Pt (610.65): C 39.34, H 6.60; found: C 39.60, H 6.61.
cis-[(Cl)2Pt(S(tBu)(CH2)6CH CH2)2] (30):[31] A flask was charged with 28
ˆ
(0.462 g, 2.31 mmol), methanol (8 mL), and a solution of K2[PtCl4] (0.326 g,
0.793 mmol) in water (10 mL). The mixture was stirred (48 h) and then
centrifuged. The supernatant was removed from a yellow oily precipitate
by pipette. Column chromatography (silica gel, twice: first 3:1 v/v hexane/
THF; second 1:1 v/v hexane/CH2Cl2) gave a yellow band which was dried
ˆ
ˆ
by oil pump vacuum to give 30 as a yellow waxy solid (0.261 g, 0.392 mmol,
(m, 2H, 2CH ), 4.98 ± 4.89 (m, 4H, 2 CH2), 2.55 ± 2.51 (m, 4H, 2PCH2),
1
ˆ
ˆ
50%). H NMR (300 MHz, CDCl3, 208C): d ˆ 5.76 (m, 2H, 2CH ), 4.94
2.02 ± 1.96 (m, 4H, 2CH2CH ), 1.62 ± 1.58 (m, 4H, 2PCH2CH2), 1.43 ± 1.25
ˆ
(m, 4H, 2 CH2), 3.39 (brm, 2H, 2SCHH'), 2.18 (brm, 2H, 2SCHH'), 2.02
(m, 4H, 2CH2CH ), 1.96 ± 1.61 (brm, 4H, 2SCH2CH2), 1.54 (s, 18H,
2C(CH3)3), 1.51 ± 1.29 (m, 12H, 6CH2); 13C{1H} NMR (75 MHz, CDCl3,
(m, 12H, 6CH2); 13C{1H} NMR (100 MHz, CDCl3, 328C, TMS): d ˆ 187.8
(dt, 1J(C,Rh) ˆ 80, J(C,P) ˆ 15 Hz, CO), 139.1 (s, CH ), 134.0 (virtual t,
2
ˆ
ˆ
J(C,P) ˆ 21 Hz,[59] i-Ph), 133.4 (virtual t, J(C,P) ˆ 6 Hz, o-Ph), 129.8 (s, p-
ˆ
ˆ
ˆ
Ph), 128.2 (virtual t, J(C,P) ˆ 6 Hz, m-Ph), 114.2 (s, CH2), 33.7 (s,
208C): d ˆ 138.9 (s, CH ), 114.3 (s, CH2), 51.5 (s, C(CH3)3), 33.7 (s,
Chem. Eur. J. 2001, 7, No. 18 ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0718-3945 $ 17.50+.50/0
3945

J. Gladysz et al.
FULL PAPER
ˆ
ˆ
-CH2CH ), 31.1 (virtual t, J(C,P) ˆ 6 Hz, CH2), 28.73 (s, CH2), 28.69 (s,
328C, TMS)[63] d ˆ 138.9 (s, CH ), 133.0 (virtual t, J(C,P) ˆ 6 Hz,[59] o-Ph),
130.8 (virtual t, J(C,P) ˆ 28 Hz, i-Ph) 130.2 (s, p-Ph) 128.0 (virtual t,
CH2), 27.2 (virtual t, J(C,P) ˆ 14 Hz, CH2), 24.9 (s, CH2); 31P{1H} NMR
(161 MHz, CDCl3, 328C): d ˆ 25.1 (d, 1J(P,Rh) ˆ 125.1 Hz) and (161 MHz,
[D6]DMSO, 328C): d ˆ 25.9 (d, 1J(P,Rh) ˆ 122.9 Hz) and (161 MHz,
C6H5Cl, 328C) 22.3 (d, 1J(P,Rh) ˆ 125.0 Hz); IR (CDCl3): nÄ ˆ 1970
ˆ
ˆ
J(C,P) ˆ 6 Hz, m-Ph), 114.3 (s, CH2), 33.7 (s, CH2CH ), 31.3 (virtual t,
J(C,P) ˆ 7 Hz, CH2), 28.8 (s, 2  intensity, CH2), 26.0 (virtual t, J(C,P) ˆ
17 Hz, CH2), 25.6 (s, CH2); 31P{1H} NMR (161 MHz, CDCl3, 328C): d ˆ
16.6 (s, 1J(P,Pt) ˆ 2659 Hz);[61] IR (neat oil): nÄ ˆ 3080, 2930, 2856, 1502,
1463, 1436, 1104, 1061, 1000, 953, 911, 803, 741, 690 cm 1; MS (FAB,
(CO) cm 1; MS (FAB, 3-NBA): m/z (%): 760 (3) [M‡H] , 730 (85) [M
‡
‡
‡
‡
CO] , 723 (30) [M Cl] , 695 (42) [M CO Cl] , 397 (90)
‡
‡
‡
‡
ˆ
ˆ
[Rh(Ph2P(CH2)6CH CH2)] , 297 (100) [Ph2P(CH2)6CH CH2] ; elemental
analysis calcd (%) for C41H50ClOP2Rh (759.1): C 64.87, H 6.64; found: C
64.74, H 6.34.
3-NBA): m/z (%): 989 (3) [M] , 954 (30) [M Cl] , 785 (20) [M Cl
‡
‡
ˆ
C6F5] ,
489
(80)
[Pt(Ph2P(CH2)6CH CH2)] ,
[Ph2P(CH2)6CH CH2] ; elemental analysis calcd (%) for C46H50ClF5P2Pt
(990.4): C 55.79, H 5.09; found: C 55.87, H 5.17.
297
(100)
‡
ˆ
ˆ
trans-[(Cl)(CO)Rh(P(Ph)2(CH2)6CH CH(CH2)6P(Ph)2)] (35): A Schlenk
ˆ
flask was charged with 34 (0.080 g, 0.105 mmol), CH2Cl2 (39 mL) and 1 (ca.
half of 0.0043 g, 0.0052 mmol, 5 mol%), and fitted with a condenser. The
solution was heated under reflux. After 2 h, the remaining 1 was added.
After 2 h, solvent was removed by rotary evaporation. Column chroma-
tography (silica gel, 14 Â 2.5 cm, 3:1 v/v CH2Cl2/hexane) gave a yellow band
which was dried by oil pump vacuum to give 35 as a yellow powder (0.064 g,
0.088 mmol, 83%; Z/E 17:83[54, 55b]). M.p. 145 ± 1468C (decomp); 1H NMR
(400 MHz, CDCl3, 328C, TMS): d ˆ 7.81 ± 7.76 (m, 8H of 4Ph), 7.37 ± 7.24
trans-[(Cl)(C6F5)Pt(P(Ph)2(CH2)6CH CH(CH2)6P(Ph)2)] (38):
A two-
necked flask was charged with CH2Cl2 (60 mL), 1 (ca. half of 0.008 g,
0.009 mmol, 7 mol%), and 37 (0.150 g, 0.151 mmol), and fitted with a
condenser. The solution was heated under reflux. After 2 h the remaining 1
was added. After 3 h, solvent was removed by rotary evaporation. The
residue was filtered through an alumina plug (5 cm) with CH2Cl2. Solvent
was removed by oil pump vacuum to give 38 as a pale pink solid (0.131 g,
0.136 mmol, 90%; Z/E 17:83[54, 55b]). M.p. 193 ± 1958C; 1H NMR (400 MHz,
CDCl3, 258C, TMS): d ˆ 7.46 ± 7.40 (m, 8H of 4Ph), 7.30 ± 7.26 (m, 12H of
[55b]
ˆ
(m, 12H of 4Ph), 5.38 ± 5.35/5.34 ± 5.30 (2m, 2H, Z/E CH CH, 17:83),
2.56 ± 2.53 (m, 4H, 2PCH2), 2.01 (m, 4H, 2CH2CH ), 1.90 (m, 4H,
ˆ
ˆ
4Ph), 5.38 ± 5.27 (m, 2H, CH CH), 2.66 ± 2.59 (m, 4H, 2PCH2), 2.25 (m,
ˆ
2PCH2CH2), 1.42 ± 1.23 (m, 12H, 6CH2) and ([D6]benzene, analogous
conditions/assignments) 7.90 ± 7.86 (m, 8H), 7.13 ± 7.07 (m, 12H), 5.59 ± 5.54/
5.54 ± 5.50 (2m, 2H, Z/E 11:89), 2.76 ± 2.71 (m, 4H), 2.20 ± 2.15 (m, 8H),
1.48 ± 1.32 (m, 12H); 13C{1H} NMR (100 MHz, CDCl3, 328C, TMS): d ˆ
187.6 (d, 1J(C,Rh) ˆ 73 Hz, CO), 134.6 (virtual t, J(C,P) ˆ 21 Hz,[59] i-Ph),
4H, 2CH2CH ), 2.05 (m, 4H, 2PCH2CH2), 1.48 ± 1.42 (m, 12H, 6CH2) and
([D6]benzene, analogous conditions/assignments) 7.67 ± 7.60 (m, 8H), 7.03 ±
6.99 (m, 12H), 5.56 ± 5.53/5.52 ± 5.49 (2m, 2H, Z/E 17:83), 2.73 ± 2.69 (m,
4H), 2.49 (m, 4H), 2.19 ± 2.18 (m, 4H), 1.57 ± 1.38 (m, 12H); 13C{1H} NMR
(100 MHz, CDCl3, 328C, TMS)[63] d ˆ 132.7 (virtual t, J(C,P) ˆ 6 Hz,[59] o-
ˆ
ˆ
133.2 (virtual t, J(C,P) ˆ 7 Hz, o-Ph), 131.0 (s, CH CH), 129.8 (s, p-Ph),
Ph), 131.8 (virtual t, J(C,P) ˆ 28 Hz, i-Ph), 131.1 (s, CH CH), 130.1 (s, p-
ˆ
ˆ
128.2 (virtual t, J(C,P) ˆ 5 Hz, m-Ph), 31.9 (s, CH2CH (E)), 31.6 (virtual t,
Ph), 128.0 (virtual t, J(C,P) ˆ 6 Hz, m-Ph), 32.0 (s, CH2CH (E)), 31.9 (s,
ˆ
J(C,P) ˆ 7 Hz, CH2), 29.2 (s, CH2CH (Z)), 28.9 (s, CH2), 28.5 (s, CH2), 27.8
CH2), 28.9 (s, CH2), 28.6 (s, CH2), 27.2 (s, CH2), 26.8 (virtual t, J(C,P) ˆ
17 Hz, CH2); 31P{1H} NMR (161 MHz, CDCl3, 328C): d ˆ 17.3/16.3[64] (2s,
1J(P,Pt) ˆ 2679/2685 Hz);[61] IR (solid film): nÄ ˆ 3057, 2926, 2853, 1502, 1459,
1436, 1104, 1058, 957, 803, 737, 690 cm 1; MS (FAB, 3-NBA): m/z (%): 961
(virtual t, J(C,P) ˆ 15 Hz, CH2), 26.7 (s, CH2); 31P{1H} NMR (161 MHz,
CDCl3, 328C): d ˆ 26.3/25.5[64] (2d, 1J(P,Rh) ˆ 125.0/125.0 Hz, 16:84); IR
(solid film): nÄ ˆ 1961 (CO) cm 1; MS (FAB, 3-NBA): m/z (%): 731 (4)
‡
‡
‡
‡
‡
‡
‡
[M] , 702 (50) [M CO] , 695 (40) [M Cl] , 665 (30) [M CO Cl] ,
(3) [M] , 926 (55) [M Cl] , 757 (20) [M Cl C6F5] , 566 (35)
‡
‡
ˆ
ˆ
565 (4) [Ph2P(CH2)6CH CH(CH2)6PPh2] ; elemental analysis calcd (%)
for C39H46ClOP2Rh (731.1): C 64.07, H 6.34; found: C 64.33, H 6.51.
[Ph2P(CH2)6CH CH(CH2)6PPh2] ; elemental analysis calcd (%) for
C44H46ClF5P2Pt (962.3): C 54.92, H 4.82; found: C 55.19, H 5.00.
trans-[(Cl)(CO)Rh(P(Ph)2(CH2)14P(Ph)2)] (36): A Fischer± Porter bottle
was charged with 35 (0.144 g, 0.156 mmol), [Rh(PPh3)3(Cl)] (0.021 g,
0.0023 mmol, 14 mol%), and toluene (23 mL), and flushed several times
with H2. The mixture was stirred under H2 (75 psig, 20 h). Solvent was
removed by oil pump vacuum. Column chromatography (silica gel, 8 Â
2.5 cm, 3:1 v/v CH2Cl2/hexane) gave a yellow band which was dried by oil
pump vacuum to give 36 as a yellow powder (0.063 g, 0.086 mmol, 55%). In
some cases, an oil was obtained which solidified when stored in a
refrigerator. If spectra showed small amounts of 35, the hydrogenation
was repeated (10% Pd/C in toluene/ethanol gave comparable results).
1H NMR (400 MHz, [D6]benzene, 328C, TMS): d ˆ 7.83 ± 7.75 (m, 8H of
4Ph), 7.14 ± 6.96 (m, 12H of 4Ph), 2.66 ± 2.63 (m, 4H, 2PCH2), 1.97 (m, 4H,
2PCH2CH2), 1.70 ± 1.22 (m, 20H, 10CH2); 13C{1H} NMR (100 MHz,
CDCl3, 328C, TMS): d ˆ 134.4 (virtual t, J(C,P) ˆ 20 Hz,[59] i-Ph), 133.1
(virtual t, J(C,P) ˆ 6 Hz, o-Ph), 129.8 (s, p-Ph), 128.2 (virtual t, J(C,P) ˆ
5 Hz, m-Ph), 30.7 (virtual t, J(C,P) ˆ 7 Hz, CH2), 29.7 (s, CH2), 27.8 (s,
CH2), 27.6 (s, CH2), 27.2 (s, CH2), 26.8 (s, CH2), 25.1 (s, CH2); 31P{1H} NMR
(161 MHz, [D6]benzene, 328C): d ˆ 26.22/26.19[64] (2d, 1J(P,Rh) ˆ 125.5/
124.9 Hz); IR (solid film): nÄ ˆ 1968 (CO) cm 1; MS (FAB, 3-NBA): m/z
trans-[(Cl)(C6F5)Pt(P(Ph)2(CH2)14P(Ph)2)] (39)
A. A Schlenk flask was charged with 38 (0.100 g, 0.104 mmol), 10% Pd/C
(0.011 g, 0.010 mmol Pd), ClCH2CH2Cl (6 mL), and ethanol (6 mL),
flushed with H2, and fitted with a balloon of H2. The mixture was stirred
for 72 h. Solvent was removed by rotary evaporation, and the residue
filtered through an alumina plug (1.5 cm) with CH2Cl2. Solvent was
removed by oil pump vacuum to give 39 as a white powder (0.094 g,
0.098 mmol, 94%). M.p. 162 ± 1648C; 1H NMR (400 MHz, CDCl3, 258C,
TMS): d ˆ 7.47 ± 7.42 (m, 8H of 4Ph), 7.31 ± 7.27 (m, 12H of 4Ph), 2.67 ± 2.61
(m, 4H, 2PCH2), 2.13 ± 2.10 (m, 4H, 2PCH2CH2), 1.50 ± 1.23 (m, 20H,
10CH2); 13C{1H} NMR (100 MHz, CDCl3, 328C, TMS)[63] d ˆ 132.8
(virtual t, J(C,P) ˆ 6 Hz,[59] m-Ph), 131.4 (virtual t, J(C,P) ˆ 28 Hz, i-Ph),
130.1 (s, p-Ph), 127.9 (virtual t, J(C,P) ˆ 5 Hz, m-Ph), 31.0 (virtual t,
J(C,P) ˆ 7 Hz, CH2), 27.7 (s, CH2), 27.6 (s, CH2), 27.2 (s, CH2), 26.5 (s,
CH2), 26.2 (virtual t, J(C,P) ˆ 17 Hz, CH2), 25.7 (s, CH2); 31P{1H} NMR
(161 MHz, CDCl3, 258C): d ˆ 17.1/16.7[64] (2s, 1J(P,Pt) ˆ 2670/2663 Hz);[61]
IR (solid film): nÄ ˆ 3057, 2926, 2856, 1502, 1459, 1436, 1104, 1061, 957, 803,
741, 691 cm 1; MS (FAB, 3-NBA): m/z (%): 964 (14) [M] , 928 (100) [M
‡
‡
‡
‡
Cl] , 760 (50) [M Cl C6F5] , 565 (16) [Ph2P(CH2)14PPh2] ; elemental
analysis calcd (%) for C44H48ClF5P2Pt (964.3): C 54.80, H 5.02; found: C
54.91, H 5.23.
‡
‡
‡
(%): 734 (10) [M‡H] , 704 (40) [M CO] , 697 (35) [M Cl] , 665 (50)
‡
‡
[M CO Cl] , 567 (100) [Ph2P(CH2)14PPh2] ; elemental analysis calcd
(%) for C39H48ClOP2Rh (733.1): C 63.90, H 6.60; found: C 63.80/63.69, H
7.00/6.23 (same sample).
B. Complex 38 (0.237 g, 0.246 mmol), 10% Pd/C (0.026 g, 0.024 mmol Pd),
ClCH2CH2Cl (13 mL), ethanol (13 mL), and H2 were combined as in
procedure A. Column chromatography of the reaction residue (alumina,
11 Â 2.5 cm, 1:1 v/v CH2Cl2/hexane) gave a product band which was dried
by oil pump vacuum to give 39 as a white powder (0.185 mg, 0.191 mmol,
72%). The 1H NMR and mass spectra were identical with those above. The
31P NMR spectrum showed only one signal. 31P{1H} NMR (161 MHz,
CDCl3/[D6]benzene 25/328C): d ˆ 17.0/17.1 (s, 1J(P,Pt) ˆ 2672/2673 Hz).[61]
ˆ
trans-[(Cl)(C6F5)Pt(PPh2(CH2)6CH CH2)2] (37): A Schlenk flask was
charged with [Pt(m-Cl)(C6F5)(SR2)]2 (0.478 g, 0.493 mmol; SR2 ˆ tetrahy-
drothiophene),[34] 12 (0.720 g, 2.43 mmol) and CH2Cl2 (30 mL). The
mixture was stirred (16 h) and filtered through a Celite plug (1 cm) and a
decolorizing charcoal plug (2 cm). Solvent was removed by oil pump
vacuum to yield 37 as a colorless oil (0.769 g, 0.776 mmol, 79%) which was
spectroscopically pure and used for further chemistry. For the analytical
sample, the Celite/carbon filtrations were replaced by column chromatog-
raphy (alumina, 10 Â 2.5 cm, CH2Cl2; 71% yield). 1H NMR (400 MHz,
CDCl3, 328C, TMS): d ˆ 7.50 ± 7.46 (m, 8H of 4Ph), 7.32 ± 7.22 (m, 12H of
ˆ
fac-[(CO)3W(PPh((CH2)6CH CH2)2)3] (41): A Schlenk flask was charged
with [(CO)3W(NCCH2CH3)3] (40; 0.310 g, 0.716 mmol),[37] 13 (0.727 g,
2.20 mmol), and CH2Cl2 (50 mL). The mixture was stirred (2 h). Solvent
removed by oil pump vacuum. Column chromatography (silica gel, 5:1 v/v
pentane/CH2Cl2) gave a yellow band which was dried by oil pump vacuum
to give 41 as a yellow solid (0.642 g, 0.510 mmol, 71%). M.p. 58 ± 618C;
ˆ
ˆ
4Ph), 5.84 ± 5.74 (m, 2H, 2CH ), 5.01 ± 4.90 (m, 4H, 2 CH2), 2.60 ± 2.54
ˆ
(m, 4H, 2PCH2), 2.05 ± 2.00 (m, 4H, 2CH2CH ), 1.97 ± 1.85 (m, 4H,
2PCH2CH2), 1.44 ± 1.30 (m, 12H, 6CH2); 13C{1H} NMR (100 MHz, CDCl3,
3946
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0718-3946 $ 17.50+.50/0
Chem. Eur. J. 2001, 7, No. 18

Olefin Metathesis
3931±3950
Table 1. General crystallographic data.
11 ´ CH2Cl2
17
(E)-22
23
formula
MW
C29H29F3NO4P2ReS ´ CH2Cl2
877.66
C30H46ClNOPRe
689.33
C41H46BrO3P2Re
914.83
C41H48BrO3P2Re
916.84
diffractometer
T [K]
Nonius MACH3
173(2)
Kuma KM4
120(2)
Nonius CAD-4
291(2)
Nonius MACH3
173(2)
l [Š]
0.71073
0.71073
0.71073
0.71073
crystal system
space group
a [Š]
b [Š]
c [Š]
a [8]
b [8]
g [8]
V [Š3]
triclinic
P1
monoclinic
P21/n
12.113(5)
19.950(6)
13.158(6)
90
109.20(4)
90
3002.8(21)
4
1.525
4.21
1392
0.2 Â 0.2 Â 0.2
2.04 to 25.00
14 to 1; 0 to 23;
15 to 15
6212
monoclinic
P21/c
18.788(6)
10.092(3)
20.495(7)
90
96.83(3)
90
3859(2)
monoclinic
P21/c
18.692(4)
10.078(2)
20.105(4)
90
97.09(3)
90
3758.3(13)
4
1.620
4.419
1832
0.20 Â 0.15 Â 0.05
2.26 to 24.97
0 to 22; 11 to 0;
23 to 23
6801
Å
9.324(2)
13.835(3)
13.896(3)
65.30(3)
86.26(3)
85.47(3)
1622.5(6)
2
Z
4
3
1calcd [Mgm
]
1.796
4.127
864
1.575
4.304
1824
0.40 Â 0.31 Â 0.22
2.00 to 25.00
0 to 22; 0 to 11;
24 to 24
6971
6753
5094
6753/1/434
1.000
1
m [mm
F(000)
crystal size [mm3]
q limit [8]
]
0.30 Â 0.30 Â 0.30
2.65 to 24.97
11 to 11; 16 to 16;
16 to 16
11874
5683
5299
5683/0/513
0.997
index ranges (h, k, l)
reflections collected
independent reflections
reflections [I > 2s(I)]
data/restraints/parameters
GOF on F2
5285
3468
5285/27/308
1.170
6587
4164
6587/28/429
1.211
final R indices [I > 2s(I)]
R1 ˆ 0.0202,
wR2 ˆ 0.0485
R1 ˆ 0.0231,
wR2 ˆ 0.0497
0.893
R1 ˆ 0.0754,
wR2 ˆ 0.0584
R1 ˆ 0.0248,
wR2 ˆ 0.0645
1.128
R1 ˆ 0.0537,
wR2 ˆ 0.1389
R1 ˆ 0.0822,
wR2 ˆ 0.1486
1.443
R1 ˆ 0.0501,
wR2 ˆ 0.1123
R1 ˆ 0.1167,
wR2 ˆ 0.1347
1.679
R indices (all data)
3
Dp (max) [eŠ
]
1H NMR (400 MHz, [D6]benzene, 328C): d ˆ 7.27, 7.14, 6.52 (3m, 15H,
fac-[(CO)3W{P(Ph)((CH2)6CH2)2}3] (43; mixture of macrocycles): A Fisher±
Porter bottle was charged with 42 (0.110 g, 0.094 mmol), [Rh(PPh3)3(Cl)]
(0.005 g, 0.005 mmol, 5 mol%), and toluene (10 mL). The mixture was
stirred under H2 (90 psig; 2d), concentrated to 1 mL, and rinsed through a
silica plug (2 cm) with CH2Cl2. The filtrate was dried by oil pump vacuum
to give 43 as a yellow powder (0.104 g, 0.088 mmol, 94%). M.p. 1598C
(decomp); 1H NMR (400 MHz, CDCl3, 328C): d ˆ 7.40 ± 6.35 (m, 15H,
3Ph), 2.02 ± 1.79 (m, 12H, 6PCH2), 1.50 ± 1.00 (m, 72H, 36CH2); 13C{1H}
NMR (100 MHz, CDCl3, 328C): d ˆ 131.0 ± 128.1 (Ph signals), 34.0 ± 23.2
(CH2 signals); 31P{1H} NMR (161 MHz, CDCl3, 328C): d ˆ 3.0 to 8.0
(m); IR (solid film): nÄ ˆ 1915, 1816 (CO) cm 1; MS (FAB, 3-NBA/CH2Cl2):
ˆ
ˆ
3Ph), 5.76 (m, 6H, 6CH ), 4.98 (m, 12H, 6 CH2), 2.21 (m, 12H,
6CH2CH ), 1.91 (m, 12H, 6PCH2), 1.62 ± 0.94 (m, 48H, 24CH2); 13C{1H}
ˆ
NMR (100 MHz, CDCl3, 328C): d ˆ 212.2 (d, 2J(C,P) ˆ 53 Hz, W(CO)3),
ˆ
140.7 (m, i-Ph), 139.1 (s, CH ), 130.4 (s, p-Ph), 128.3 (m, o-Ph), 127.9 (m, m-
ˆ
ˆ
Ph), 114.2 (s, CH2), 33.7 (s, CH2CH ), 31.0 (s, CH2), 29.0 (br, tentative,
CH2), 28.8 (s, CH2), 28.7 (s, CH2), 23.5 (s, CH2); 31P{1H} NMR (161 MHz,
CDCl3, 328C): d ˆ -7.6 (s, 1J(P,W) ˆ 215 Hz);[61] IR (solid film): nÄ ˆ 1915,
1810 (CO) cm 1; MS (FAB, 3-NBA/CH2Cl2): m/z (%): 1259 (10) [M] , 1231
(2) [M CO] , 1120 (5) [M CO C8H15] , 926 (10) [M
PhP(CH2)6CH CH2)2] , 332 (100) [PhP(CH2)6CH CH2)2] ; elemental
analysis calcd (%) for C69H105O3P3W (1259.36): C 65.81, H 8.40; found: C
65.81, H 8.60.
‡
‡
‡
‡
‡
ˆ
ˆ
‡
‡
‡
m/z (%): 1180 (70) [M] , 1152 (20) [M CO] , 1124 (10) [M 2CO] ;
elemental analysis calcd (%) for C63H99O3P3W (1181.22): C 64.06, H 8.45;
found: C 63.99, H 8.48.
ˆ
fac-[(CO)3W{P(Ph)((CH2)6CH )2}3] (42; mixture of macrocycles a, b, c in
Crystallography: A CH2Cl2 solution of 11 was layered with hexane and kept
at 48C. After 2 d, yellow prisms of 11 ´ (CH2Cl2) were collected by filtration.
Red prisms of 17 were grown by slow evaporation of a CH2Cl2 solution
(room temperature). One was polished with xylene to a spherical shape.
Colorless prisms of (E)-22 and (E)-25 were obtained by slow evaporation of
CH2Cl2/hexane solutions (days, room temperature). Colorless prisms of 23
were obtained by slow evaporation of a CH2Cl2/ethanol solution (weeks,
room temperature). A toluene solution of 39 was layered with ethanol and
kept at 208C. After two days, a colorless prism was removed. Colorless
needles of 42a' were grown by slow evaporation of a CH2Cl2 solution (room
temperature). The sample was not homogeneous (powder and other crystal
morphologies were present), and was recrystallized from CH2Cl2/hexane to
give another heterogeneous sample, from which a colorless prism of 42a'' ´
(C6H14)0.5 was extracted.
Scheme 9): A Schlenk flask was charged with 41 (0.131 g, 0.104 mmol) and
CH2Cl2 (250 mL), and fitted with a condenser. The solution was heated
under reflux, and about half of a solution of 1 (0.008 g, 0.009 mmol, 9 mol%
ˆ
or 3 mol% per product C C) in CH2Cl2 (4 mL) was added. After 2 h, the
remaining 1 was added. After another 2 h, solvent was removed by rotary
evaporation. The residue was filtered through a silica plug (2 cm) with
CH2Cl2. The filtrate was concentrated to
a yellow solid. Column
chromatography (silica gel, 3:1 v/v pentane/CH2Cl2) gave a yellow band
which was dried by oil pump vacuum to give 42 as a yellow powder (0.098 g,
0.083 mmol, 83%). M.p. 2058C (decomp);[18] 1H NMR (400 MHz, CDCl3,
ˆ
328C): d ˆ 7.3 ± 6.4 (m, 15H, 3Ph), 5.30 (m, 6H, 3CH CH), 2.04 (m, 12H,
ˆ
6CH2CH ), 2.00 ± 1.80 (m, 12H, 6PCH2), 1.60 ± 0.94 (m, 48H, 24CH2);
13C{1H} NMR (100 MHz, CDCl3, 328C): d ˆ 131.2 ± 127.8 (Ph and CH ˆ
signals), 34.0 ± 23.2 (CH2 signals); 31P{1H} NMR (161 MHz, CDCl3, 328C):
d ˆ 3.0 to 8.0 (m); IR (solid film): nÄ ˆ 1922, 1818 (CO) cm 1; MS (FAB,
Data were collected as summarized in Table 1. Cell parameters were
determined and refined from 15 reflections for 11 ´ (CH2Cl2), 23, and 25, 73
reflections for 17, 25 reflections for (E)-22, and 50 reflections for 42a' and
42a'' ´ (C6H14)0.5. Cell parameters for 39 were obtained from 10 frames
using a 108 scan and refined with 9668 reflections. Space groups were
‡
‡
3-NBA/CH2Cl2): m/z (%): 1174 (100) [M] , 1146 (40) [M CO] , 1118 (15)
‡
‡
ˆ
[M 2CO] , 905 (10) [(P(Ph)(CH2)6CH CH(CH2)6)3] , 814 (10) [M
‡
ˆ
ˆ
(P(Ph)(CH2)6CH CH(CH2)6)2 2CO] , 605 (10) [(P(Ph)(CH2)6CH
‡
‡
ˆ
CH(CH2)6)2] , 303 (25) [P(Ph)(CH2)6CH CH(CH2)6] .
Chem. Eur. J. 2001, 7, No. 18
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0718-3947 $ 17.50+.50/0
3947

J. Gladysz et al.
FULL PAPER
Table 1 cont.
(E)-25
39
42a'
42a'' ´ (C6H14)0.5
formula
MW
C38H46Cl2P2Pt
830.68
C44H48ClP2F5Pt
964.33
C63H93O3P3W
1175.13
C63H93O3P3W´ 0.5C6H14
1218.22
diffractometer
T [K]
Nonius MACH3
173(2)
Nonius KappaCCD
173(2)
Kuma KM4
95(2)
Kuma KM4
100(2)
l [Š]
0.71073
0.71073
0.71073
0.71073
crystal system
space group
a [Š]
b [Š]
c [Š]
a [8]
b [8]
g [8]
V [Š3]
triclinic
P1
monoclinic
C2/c
31.7963(7)
10.7342(3)
24.9213(6)
90
102.2800(10)
90
8311.2(4)
8
hexagonal
P3
18.900(8)
18.900(8)
9.842(3)
90
90
120
3045(2)
2
1.282
2.017
1228
0.20 Â 0.15 Â 0.05
2.99 to 26.99
25 to 12; 0 to 25;
0 to 12
14105
3555
3224
3555/0/211
1.277
triclinic
P1
Å
Å
Å
10.105(2)
13.837(3)
14.100(3)
71.32(3)
85.11(3)
71.25(3)
1768.1(6)
2
10.659(4)
16.353(5)
20.183(7)
109.78(3)
97.90(3)
103.00(3)
3136.9(19)
2
Z
3
1calcd [Mgm
]
1.560
4.235
832
1.541
3.570
3856
1.290
1.960
1278
1
m [mm
F(000)
crystal size [mm3]
q limit [8]
]
0.30 Â 0.30 Â 0.20
2.44 to 24.97
12 to 11; 16 to 15;
16 to 0
6481
6206
5423
6206/0/388
1.034
0.2 Â 0.2 Â 0.1
1.31 to 27.50
41 to 41; 12 to 13;
32 to 32
15944
9273
4884
9273/44/486
0.998
0.15 Â 0.06 Â 0.04
3.32 to 27.50
11 to 13; 21 to 21;
23 to 23
21612
13477
6634
13477/64/658
0.994
index ranges (h, k, l)
reflections collected
independent reflections
reflections [I > 2s(I)]
data/restraints/parameters
GOF on F2
final R indices [I > 2s(I)]
R1 ˆ 0.0274,
wR2 ˆ 0.0656
R1 ˆ 0.0375,
wR2 ˆ 0.0705
1.631
R1 ˆ 0.0435,
wR2 ˆ 0.0913
R1 ˆ 0.1207,
wR2 ˆ 0.1278
1.885
R1 ˆ 0.1018,
wR2 ˆ 0.1576
R1 ˆ 0.1196,
wR2 ˆ 0.1647
1.374
R1 ˆ 0.0833,
wR2 ˆ 0.0875
R1 ˆ 0.1695,
wR2 ˆ 0.1041
1.451
R indices (all data)
3
Dp (max) [eŠ
]
determined from systematic absences and subsequent least-squares refine-
ments. Lorentz, polarization, and empirical absorption corrections were
applied (11 ´ (CH2Cl2), (E)-22, 23, and (E)-25, f scans; 17, 42a', and 42a'' ´
(C6H14)0.5, numerical by use of SHELX-76[65]; 39, other[66]).
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft (DFG; GL 300-1/1), the
US NSF, and Polish State Committee for Scientific Research
Â
(3T09A00119) for support, the Ministerio de Educacion y Ciencia (Spain)
The structures of 11 ´ (CH2Cl2), 23, and (E)-25 were solved by direct
methods (SHELXS-86). The parameters were refined with all data by full-
matrix-least-squares on F2 (SHELXL-93).[67] Non-hydrogen atoms were
refined anisotropically. The hydrogen atoms were fixed in idealized
positions (riding model). Two atoms of 23 showed displacement disorder
(C3/C3' and C5/C5'), which could be solved and refined to a 87:13
occupancy ratio. The structure of 39 was similarly solved and refined
(SHELXS-97, SHELXL-97).[68] Two atoms showed displacement disorder
(C10/C10' and C11/C11'), which could be solved and refined to a 55:45
occupancy ratio. The immediately adjacent atoms gave larger thermal
ellipsoids, but two distinct positions could not be resolved.
and the Fulbright Commission for Fellowships (J.M.M.-A.), and Johnson
Matthey PMC for precious metal loans.
[1] A recent overview: A. Fürstner, Angew. Chem. 2000, 112, 3140;
Angew. Chem. Int. Ed. 2000, 39, 3012.
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Chem. Commun. 1997, 2053; b) G. Rapenne, C. Dietrich-Buchecker,
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[6] a) J. M. Martín-Alvarez, F. A. Hampel, A. M. Arif, J. A. Gladysz,
Organometallics 1999, 18, 955; b) E. B. Bauer, J. Ruwwe, J. M. Martín-
Alvarez, T. B. Peters, J. C. Bohling, F. A. Hampel, S. Szafert, T. Lis,
J. A. Gladysz, J. Chem. Soc. Chem. Commun. 2000, 2261.
The structures of 17, 42a', and 42a'' ´ (C6H14)0.5 were solved by standard
heavy atom techniques (SHELXS-97) and refined with SHELXL-97. Non-
hydrogen atoms were refined with anisotropic thermal parameters, except
the following which showed non-positive definition: C21 C27, C31 C37,
C21A C27A, and C31A C37A of 17 (cocrystallizing Z/E isomers that refined
to a 58:42 ratio); C(14A), C(15A), C(16A), C(17A), C(27A), C(26A),
C(25A), C(24A), and C(23A) of 42a'' ´ (C6H14)0.5. The hydrogen atoms were
fixed in idealized positions (riding model). The structure of (E)-22 was
similarly solved and refined (MOLEN VAX package[69] and SHELX-97).
Scattering factors, and Df' and Df'' values, were taken from literature.[70]
All data (except structure factors) have been deposited with the Cambridge
Crystallographic Data Centre in association with earlier communications
((E)-22,[6a] 23,[6a] (E)-25,[6a] 39,[6b] 42a'[6b]) or as supplementary publications
CCDC-148294 (11 ´ (CH2Cl2)), CCDC-148297 (17), and CCDC-148298
(42a'' ´ (C6H14)0.5). Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax:
(‡44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
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3948
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0718-3948 $ 17.50+.50/0
Chem. Eur. J. 2001, 7, No. 18

Olefin Metathesis
3931±3950
Sültemeyer, K. H. Dötz, H. Hupfer, M. Nieger, J. Organomet. Chem.
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common experience from the synthesis methods employed, we
emphasize that our spectroscopic data do not rigorously exclude trans
isomers. Far-IR spectra are often diagnostic,[29, 30b] but that of a
representative compound 30 was (in our opinion) not, perhaps due to
the presence of meso/rac isomers (spectra of 31 ± 33 would be further
complicated by Z/E isomers).
[8] T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
Â
Â
[9] F. Agbossou, E. J. OꢀConnor, C. M. Garner, N. Quiros Mendez, J. M.
Â
Fernandez, A. T. Patton, J. A. Ramsden, J. A. Gladysz, Inorg. Synth.
1992, 29, 211.
[10] J. J. Kowalczyk, A. M. Arif, J. A. Gladysz, Chem. Ber. 1991, 124, 729.
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Rev. 2001, 101, 1031.
Â
[33] M.-A. Guillevic, C. Rocaboy, A. M. Arif, I. T. Horvath, J. A. Gladysz,
[12] All isomer ratios are normalized to 100. For NMR determinations,
error limits on each component are generally Æ2 (e.g., 23:77 Â (23 Æ
2):(77 Æ 2)).
Organometallics 1998, 17, 707.
Â
Â
Ä
[34] R. Uson, J. Fornies, P. Espinet, R. Navarro, C. Fortuno, J. Chem. Soc.
Dalton Trans. 1987, 2077.
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[13] K. M. Nicholas, J. Am. Chem. Soc. 1975, 97, 3254.
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preceding papers report successful metatheses of olefinic thioethers
with Schrock-type catalysts.
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M. D. E. Forbes, J. T. Patton, T. L. Myers, H. D. Maynard, D. W. Smith,
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[48] E. Bauer, J. A. Gladysz, unpublished results.
[18] A correct microanalysis of this compound was not obtained.
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[23] We believe that E isomers likely dominate with 16 and 17 (44 ± 42:56 ±
58 Z/E), but the data are equivocal and the Z isomer dominates in
crystalline 17 (58:42 Z/E).
[24] A. Fürstner in Templated Organic Synthesis (Eds.: F. Diederich, P.
Stang), Wiley-VCH, New York, 2000, p. 249.
[25] The intermediate methyl complex [(h5-C5Me5)Re(NO)(P(Ph)-
ˆ
(CH2)6CH CH(CH2)6)(CH3)] was partially characterized, but could
not be obtained in analytically pure form. Selected data are as follows.
1H NMR (400 MHz, [D6]benzene, 328C): d ˆ 5.42 ± 5.25 (m, 2H,
ˆ
ˆ
CH CH), 2.40 ± 2.01 (m, 4H, PCH2), 2.01 ± 1.71 (m, 4H, CH2CH ),
1.56/1.55 (2s, 15H, C5(CH3)5), 1.43 ± 1.14 (m, 16H, CH2), 1.34/1.31 (2d,
2J(P,C) ˆ 6 Hz, 3H, CH3); 13C{1H} NMR (100 MHz, [D6]benzene,
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assigned to the meta aryl carbon: B. E. Mann, J. Chem. Soc. Perkin
Trans. 2 1972, 20.
ˆ
328C): d ˆ 97.0/96.9 (2s, C5(CH3)5), 36.0/35.5 (2s, CH2CH ), 10.0/9.9
(2s, C5(CH3)5), 27.2/ 27.4 (2d, 1J(P,C) ˆ 7 Hz, ReCH3); 31P{1H}
NMR (161 MHz, [D6]benzene, 328C): d ˆ 5.34/ 5.92 (2s); IR
1
(solid film): nÄ ˆ 1606 (NO) cm
.
[26] A. M. Bond, R. Colton, M. E. McDonald, Inorg. Chem. 1978, 17, 2842.
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ˆ
[28] a) W. E. Hill, D. M. A. Minahan, J. G. Taylor, C. A. McAuliffe, J. Am.
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[54] The Z/E assignment is based upon the chemical shift of the CH2CH
13
[11]
ˆ
C NMR signal (downfield E).
[55] The Z/E isomer ratio was quantified by a) 1H homodecoupling of the
ˆ
ˆ
CH2CH signal to simplify the CH CH multiplets, which were
integrated; b) direct integration of separated CH CH multiplets;
ˆ
c) integration of the 31P NMR signals.
Chem. Eur. J. 2001, 7, No. 18
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3949

J. Gladysz et al.
FULL PAPER
[56] M. Antberg, C. Prengel, L. Dahlenburg, Inorg. Chem. 1984, 23, 4170.
[57] The PCH2CH2CH2 13C NMR signals were assigned from chemical shift
and coupling constant patterns established previously: W. E. Hill,
D. M. A. Minahan, J. G. Taylor, C. A. McAuliffe, J. Chem. Soc. Perkin
2 1982, 327.
[58] S. P. Schmidt, W. C. Trogler, F. Basolo, Inorg. Synth. 1989, 23, 41 (the
checkerꢀs modification was employed).
[59] P. S. Pregosin, L. M. Venanzi, Chem. Br. 1978, 276. The apparent
coupling between adjacent peaks of the triplet is given.
[60] H. C. Clark, L. E. Manzer, J. Organomet. Chem. 1973, 59, 411.
[65] G. M. Sheldrick, SHELX-76, University of Cambridge, UK, 1976.
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packº data processing software: Z. Otwinowski, W. Minor, Methods
Enzymol. 1997, 276, 307.
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Press, Delft, Holland, 1978, pp. 64 ± 71.
[61] This coupling represents
a
satellite (d; 195Pt ˆ 33.8% or 183Wˆ
14.3%), and is not reflected in the peak multiplicity given.
[62] J. Chatt, L. M. Venanzi, J. Chem. Soc. 1957, 1735.
[63] The C6F5 signals were too weak for complete assignment.
[64] This signal was tentatively assigned to a dimeric product (ca. 15%)
derived from intermolecular metathesis.
[70] D. T. Cromer, J. T. Waber, in International Tables for X-ray Crystal-
lography (Eds.: J. A. Ibers, W. C. Hamilton), Kynoch, Birmingham,
England, 1974.
Received: April 2, 2001 [F3172]
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