Alkene Metatheses in Transition Metal Coordination Spheres: Effect of Ring Size and Substitution on the Efficiencies of Macrocyclizations that Join Trans Positions of Square-Planar Platinum Complexes

Article abstract of DOI:10.1021/om034121u

Reactions of KPPh₂ and Br(CH₂)_nCH=CH ₂ give the phosphines PPh₂(CH₂) _nCH=CH₂ (n = a, 4; b, 6; c, 8; d, 9; 95-41%), which are combined with the platinum tetrahydrothiophene complex [Pt(μ-Cl)(C ₆F₅)(S(CH₂CH₂-)₂)] ₂ to give trans-(Cl)(C₆F₅)Pt(PPh ₂(CH₂)_nCH=CH₂)₂ (3a-d, 71-54%). When treated with Grubbs' catalyst, ring-closing alkene metatheses occur to give 13- to 23-membered macrocycles with trans-spanning diphosphine ligands (96-85%, including some dimeric or oligomeric byproducts). The mixtures of C=C isomers are hydrogenated (1 atm, 10% Pd/C) to give trans-(Cl)(C ₆F₅)Pt(PPh₂(CH₂) _2n+2PPh₂) (6a-d), which are isolated in 72-50% yields. Comparable results are obtained with (1) the second-generation dihydroimidazolylidene Grubbs' catalyst and (2) a series of compounds derived from the dimethylated phosphine Ph₂P(CH₂) ₂C(CH₃)₂(CH₂)₃CH=CH ₂, in turn prepared by sequential reactions of BrCH ₂CH₂C(CH₃)₂CH₂CH ₂Br with BrMgCH₂CH=CH₂/Li₂CuCl ₄ and KPPh₂. The crystal structures of 6a-d are analyzed, but no special features that would promote intramolecular macrocyclizations are noted. A reaction of [Pt(μ-Cl)(C₆F₅)(S(CH ₂CH₂-)₂)]₂ and the diphosphine Ph₂P(CH₂)₁₄PPh₂ leads to a multitude of products and little 6b (<15%).

Full text of DOI:10.1021/om034121u

Organometallics 2003, 22, 5567-5580
5567
Alk en e Meta th eses in Tr a n sition Meta l Coor d in a tion
Sp h er es: Effect of Rin g Size a n d Su bstitu tion on th e
Efficien cies of Ma cr ocycliza tion s Th a t J oin tr a n s
P osition s of Squ a r e-P la n a r P la tin u m Com p lexes
Eike B. Bauer, Frank Hampel, and J . A. Gladysz*
Institut fu¨r Organische Chemie, Friedrich-Alexander-Universita¨t Erlangen-Nu¨rnberg,
Henkestrasse 42, 91054 Erlangen, Germany
Received August 22, 2003
Reactions of KPPh2 and Br(CH2)nCHdCH2 give the phosphines PPh2(CH2)nCHdCH2 (n )
a , 4; b, 6; c, 8; d , 9; 95-41%), which are combined with the platinum tetrahydrothiophene
complex [Pt(µ-Cl)(C6F5)(S(CH2CH2-)2)]2 to give trans-(Cl)(C6F5)Pt(PPh2(CH2)nCHdCH2)2 (3a -
d , 71-54%). When treated with Grubbs’ catalyst, ring-closing alkene metatheses occur to
give 13- to 23-membered macrocycles with trans-spanning diphosphine ligands (96-85%,
including some dimeric or oligomeric byproducts). The mixtures of CdC isomers are
hydrogenated (1 atm, 10% Pd/C) to give trans-(Cl)(C6F5)Pt(PPh2(CH2)2n+2PPh2) (6a -d ), which
are isolated in 72-50% yields. Comparable results are obtained with (1) the second-
generation dihydroimidazolylidene Grubbs’ catalyst and (2) a series of compounds derived
from the dimethylated phosphine Ph2P(CH2)2C(CH3)2(CH2)3CHdCH2, in turn prepared by
sequential reactions of BrCH2CH2C(CH3)2CH2CH2Br with BrMgCH2CHdCH2/Li2CuCl4 and
KPPh2. The crystal structures of 6a -d are analyzed, but no special features that would
promote intramolecular macrocyclizations are noted. A reaction of [Pt(µ-Cl)(C6F5)(S(CH2-
CH2-)2)]2 and the diphosphine Ph2P(CH2)14PPh2 leads to a multitude of products and little
6b (<15%).
Sch em e 1. Syn th eses of Meta lla m a cr ocycles via
Alk en e Meta th esis
In tr od u ction
Alkene metathesis is being increasingly utilized in the
synthesis of metal-containing molecules.1 At the same
time, there is growing interest in various types of metal-
containing macrocycles and improved strategies for their
synthesis.2-4 Targets include both metallo- and metal-
lamacrocycles, which are furthermore in many cases
topologically novel. These themes were first combined
by Sauvage, who developed elegant syntheses of cat-
enanes via metathesis reactions of the type depicted
schematically in Scheme 1A (top).5 Macrocyclization
methods that had been traditionally employed in or-
ganic synthesis gave inferior results. However, alterna-
tive cyclization modes as well as intermolecular reac-
tions are possible, and the ring size and substituents
play critical roles in the success of a given reaction.
(1) Bauer, E. B.; Gladysz, J . A. In Handbook of Metathesis; Grubbs,
R. H., Ed.; Wiley-VCH: Weinheim, Germany, 2003; Vol. 2, pp 403-
431.
(2) Dietrich-Buchecker, C. O.; Sauvage, J .-P. Chem. Rev. 1987, 87,
795.
(3) Bessel, C. A.; Aggarwal, P.; Marschilok, A. C.; Takeuchi, K. J .
Chem. Rev. 2001, 101, 1031.
We and others have also generated a variety of
unusual metallo- and metallamacrocycles via alkene
metathesis,6-8 and a representative reaction type is
(4) Pecoraro, V. L.; Stemmler, A. J .; Gibney, B. R.; Bodwin, J . J .;
Wang, H.; Kampf, J . W.; Barwinski, A. Prog. Inorg. Chem. 1997, 45,
83.
(6) (a) Mart´ın-Alvarez, J . M.; Hampel, F. A.; Arif, A. M.; Gladysz,
J . A. Organometallics 1999, 18, 955. (b) Bauer, E. B.; Ruwwe, J .;
Mart´ın-Alvarez, J . M.; Peters, T. B.; Bohling, J . C.; Hampel, F. A.;
Szafert, S.; Lis, T.; Gladysz, J . A. Chem. Commun. 2000, 2261. (c)
Ruwwe, J .; Mart´ın-Alvarez, J . M.; Horn, C. R.; Bauer, E. B.; Szafert,
S.; Lis, T.; Hampel, F.; Cagle, P. C.; Gladysz, J . A. Chem. Eur. J . 2001,
7, 3931.
(7) Chuchuryukin, A. V.; Dijkstra, H. P.; Suijkerbuijk, B. M. J . M.;
Klein Gebbink, R. J . M.; van Klink, G. P. M.; Mills, A. M.; Spek, A. L.;
van Koten, G. Angew. Chem., Int. Ed. 2003, 42, 228; Angew. Chem.
2003, 115, 238.
(5) (a) Weck, M.; Mohr, B.; Sauvage, J .-P.; Grubbs, R. H. J . Org.
Chem. 1999, 64, 5463. (b) Dietrich-Buchecker, C.; Rapenne, G.;
Sauvage, J .-P. Chem. Commun. 1997, 2053. (c) Dietrich-Buchecker,
C.; Sauvage, J .-P. Chem. Commun. 1999, 615. (d) Rapenne, G.;
Dietrich-Buchecker, C.; Sauvage, J .-P. J . Am. Chem. Soc. 1999, 121,
994. (e) Belfrekh, N.; Dietrich-Buchecker, C.; Sauvage, J .-P. Inorg.
Chem. 2000, 39, 5169. (f) Mobian, P.; Kern, J .-M.; Sauvage, J .-P. J .
Am. Chem. Soc. 2003, 125, 2016.
10.1021/om034121u CCC: $25.00 © 2003 American Chemical Society
Publication on Web 11/26/2003

5568 Organometallics, Vol. 22, No. 26, 2003
Sch em e 2. Syn th eses of P la tin a m a cr ocycles
Bauer et al.
depicted schematically in Scheme 1B (bottom). Here two
alkene-containing monophosphine ligands, trans-dis-
posed about a 16-valence-electron, square-planar plati-
num or rhodium, are joined to generate a novel trans-
spanning diphosphine complex.3 However, in this as
well as several related reactions, the length of the bridge
was not varied. The monophosphines always featured
(CH2)6CHdCH2 moieties, resulting in 17-membered
macrocycles. Thus, the obvious question whether the six
methylene groups between the donor atom and terminal
alkene constitute a lucky starting point or “magic”
number has remained unanswered.
as viscous colorless liquids in 95-41% yields after
workup. The bromoalkenes 1a ,b,d were commercially
available, and 1c was prepared from the corresponding
alcohol by a slight modification of literature proce-
dures.11 The phosphines 2a -d were stable in air on the
time scale of hours, and the preparation of 2b (and all
other compounds in the b series) has been described
previously.6c,12 The synthesis of 2d was developed by
W. Mohr.13
Accordingly, we sought to systematically vary the
number of methylene groups in such trans-macrocy-
clizations and better define the limits of ring sizes that
can be accessed. Of the square-planar systems studied
previously,6 platinum complexes were selected for their
robustness and ease of crystallization. In this paper, we
report the synthesis of a series of compounds of the
formula trans-(Cl)(C6F5)Pt(PPh2(CH2)nCHdCH2)2 and
subsequent alkene metatheses that yield platinamac-
rocycles with rings ranging from 13 to 23 atoms. Each
of these are, after CdC hydrogenation, structurally
characterized. We also describe the effect of replacing
one methylene group of the (CH2)n segment by a geminal
dimethyl group. In many circumstances, geminal dialkyl
groups increase the efficiency of cyclization.9,10
The phosphines 2a ,c,d were combined with the
platinum tetrahydrothiophene complex [Pt(µ-Cl)(C6F5)-
(S(CH2CH2-)2)]2 under conditions used for 2b ear-
14
lier.15 As shown in Scheme 2, workups gave the bis-
(phosphine) complexes trans-(Cl)(C6F5)Pt(PPh2(CH2)n-
CHdCH2)2 (3a ,c,d ) as colorless oils in 71-54% yields.
They solidified over the course of several days. The new
phosphines and platinum complexes were characterized
by NMR (1H, 13C, 31P), IR, mass spectroscopy, and
microanalyses, as summarized in the Experimental
Section. Upon phosphine ligand coordination, the PCH2
1H NMR signals shift to lower field (ca. δ 2.1 to ca. δ
2.6). Other properties were very similar to those re-
Resu lts
1. Sta r tin g Com p lexes. As shown in eq 1, reactions
of the bromoalkenes Br(CH2)nCHdCH2 (1; n ) a , 4; b,
6; c, 8; d , 9) and commercial KPPh2 afforded the
requisite monophosphines PPh2(CH2)nCHdCH2 (2a -d )
(11) (a) Kobayashi, Y.; Okui, H. J . Org. Chem. 2000, 65, 612. (b)
Kamat, V. P.; Hagiwara, H.; Katsumi, T.; Hoshi, T.; Suzuki, T.; Ando,
M. Tetrahedron 2000, 56, 4397. (c) Singh, A.; Markowitz, M. A. New
J . Chem. 1994, 18, 377.
(12) Complete experimental procedures for previously reproted
compounds (b series)6c are provided in the Supporting Information.
Spectroscopic and related data are repeated in the Experimental
Section to facilitate comparisons with the new homologues (a , c, d , e
series).
(8) (a) Stahl, J .; Bohling, J . C.; Bauer, E. B.; Peters, T. B.; Mohr,
W.; Mart´ın-Alvarez, J . M.; Hampel, F.; Gladysz, J . A. Angew. Chem.,
Int. Ed. 2002, 41, 1872; Angew. Chem. 2002, 114, 1951. (b) Horn, C.
R.; Mart´ın-Alvarez, J . M.; Gladysz, J . A. Organometallics 2002, 21,
5386.
(13) Mohr, W. Doctoral Thesis, University of Erlangen-Nuremberg,
2002.
(9) Sammes, P. G.; Weller, D. J . Synthesis 1995, 1205.
(10) Forbes, M. D. E.; Patton, J . T.; Myers, T. L.; Maynard, H. D.;
Smith, D. W., J r.; Schulz, G. R.; Wagener, K. B. J . Am. Chem. Soc.
1992, 114, 10978.
(14) Uso´n, R.; Fornie´s, J .; Espinet, P.; Alfranca, G. Synth. React.
Inorg. Met.-Org. Chem. 1980, 10, 579.
(15) Uso´n, R.; Fornie´s, J .; Espinet, P.; Navarro, R.; Fortun˜o, C. J .
Chem. Soc., Dalton Trans. 1987, 2077.

Metallamacrocycles via Alkene Metatheses
Organometallics, Vol. 22, No. 26, 2003 5569
Ta ble 1. Gen er a l Cr ysta llogr a p h ic Da ta
6a
6b
6c
6d ‚(toluene)0.5
formula
fw
C
40H40ClF5P2Pt
C44H48ClF5P2Pt
964.33
Nonius KappaCCD
173(2)
0.71073
monoclinic
C2/ c
31.7963(7)
10.7342(3)
24.9213(6)
90
C48H56ClF5P2Pt
1020.41
Nonius KappaCCD
173(2)
0.71073
orthorhombic
Pbca
18.8320(2)
15.71700(10)
31.3740(4)
90
C50H60ClF5P2Pt‚(C7H8)0.5
1094.02
Nonius KappaCCD
173(2)
0.71073
monoclinic
C2/ c
31.6164(3)
10.90640(10)
32.1159(3)
90
908.02
diffractometer
temperature [K]
wavelength [Å]
cryst syst
space group
a [Å]
Nonius KappaCCD
173(2)
0.71073
monoclinic
P21/c
15.5388(1)
17.8699(1)
27.5950(2)
90
b [Å]
c [Å]
R [deg]
â [deg]
99.4800(2)
90
102.2800(10)
90
90
90
111.2526(3)(3)
90
γ [deg]
V [Å3]
7557.84(8)
8
8311.2(4)
8
9286.16(17)
8
10321.09(17)
8
Z
F
calc [Mg/m3]
1.596
1.541
1.460
1.408
abs coeff [mm-1
]
3.921
3.570
3.200
2.884
F(000)
3600
3856
4112
4436
cryst size [mm3]
θ limit [deg]
0.25 × 0.20 × 0.20
1.33 to 27.48
-19 to 19; -22 to 23;
-35 to 35
32 517
0.2 × 0.2 × 0.1
1.31 to 27.50
-41 to 41; -12 to -13;
-32 to -32
15 944
0.30 × 0.30 × 0.20
1.30 to 27.51
-24 to 24; -20 to 20;
-40 to 40
19 819
0.25 × 0.20 × 0.20
1.36 to 27.48
-40 to 40; -12 to 14;
-41 to 41
21 617
index ranges (h, k, l)
no. of reflns collected
no. of indep reflns
no. of reflns [I > 2σ(I)]
no. of data/restraints/params
goodness-of-fit on F2
17 232
13 002
17 232/0/883
1.049
9273
4884
9273/44/486
0.998
10 580
11 719
9999
11 719/122/523
1.129
15 080/0/514
1.099
final R indices [I>2σ(I)]
R1 ) 0.0329,
wR2 ) 0.0754
R1 ) 0.0559,
wR2 ) 0.0917
1.082
R1 ) 0.0435,
wR2 ) 0.0913
R1 ) 0.1207,
wR2 ) 0.1278
1.885
R1 ) 0.0354,
wR2 ) 0.0930
R1 ) 0.0590,
wR2 ) 0.1072
1.084
R1 ) 0.0515,
wR2 ) 0.1423
R1 ) 0.0628,
wR2 ) 0.1540
1.705
R indices (all data)
∆p (max) [e/Å3]
The dominant 31P NMR signal in each isolated sample
represented 88-54% of the total peak area. The mass
spectra (FAB) showed weak molecular ions and stronger
ions derived from loss of chloride and/or pentafluorophe-
nyl groups. No ions derived from dimers or oligomers
were detected. With 5a -c, for which NMR spectra
suggested fewer byproducts, two groups of dCH 1H
NMR signals could be discerned (∆δ ca. 0.15 ppm,
CDCl3). The major signal was tentatively assigned to
the E CdC isomer, in accord with our past experience
in such macrocyclizations (5a, downfield; 5b,c, upfield).6a
In all cases, the chemical shift of the CH2CHd 13C NMR
signal, another sensitive probe of E/Z stereochemistry,17
was constant and in the expected range (31.7-32.1
ppm). Integration of the dCH resonances indicated 90:
10 to 80:20 E/Z mixtures. The CdC 13C NMR signals of
the smallest macrocycle 5a were in the range of those
of 5b-d (130.9 vs 131.1-130.7 ppm), suggesting no
special interactions with the platinum. In all cases, the
major components could be further purified by careful
column chromatography. However, this came at the
expense of considerable material loss.
F igu r e 1. Alkene metathesis catalysts employed.
ported for the bis(triarylphosphine) complexes trans-
(Cl)(C6F5)Pt(PAr3)2.16
2. Title Rea ction s. Alkene metatheses were con-
ducted under conditions analogous to those previously
used for 3b.6c The initial experiments utilized Grubbs’
catalyst 4, which is depicted in Figure 1. As shown in
Scheme 2, CH2Cl2 solutions of 3a -d (ca. 0.0025 M) and
4 (5-7 mol %, added in two portions) were refluxed for
4-5 h. The solvent was removed, and the crude mix-
tures were assayed by NMR. The 1H NMR spectra
showed no terminal alkene residues, indicating metath-
esis to be g98% complete. The 31P NMR spectra showed
two to five signals, with the dominant one representing
87-48% of the total peak area, as summarized in
Scheme 2. The reaction mixtures were filtered through
alumina to separate the catalyst residue. This gave the
To simplify analysis, the samples of 5a -d were
hydrogenated (1 atm) using 10% Pd/C as catalyst. The
mixtures were filtered through alumina to give the
crude saturated macrocycles trans-(Cl)(C6F5)Pt(PPh2-
(CH2)2n+2PPh2) (6a -d ), together with any dimeric and
1
oligomeric species (94-76% total yields). The H NMR
target macrocycles trans-(Cl)(C6F5)Pt(PPh2(CH2)nCHd
spectra showed that all double bonds had been hydro-
genated. The 31P NMR spectra showed one major
product and various minor products, as summarized in
Scheme 2. Careful column chromatography afforded
spectroscopically and analytically pure 6a -d in 72-50%
CH(CH2)nPPh2) (5a -d ), together with byproducts be-
lieved to be dimers and/or oligomers arising from
intermolecular metathesis, in 96-85% yields.
(16) Mohr, W.; Stahl, J .; Hampel, F.; Gladysz, J . A. Chem. Eur. J .
2003, 9, 3324.
(17) Fu¨rstner, A.; Langemann, K. Synthesis 1997, 792.

5570 Organometallics, Vol. 22, No. 26, 2003
Bauer et al.
F igu r e 2. Molecular structures of platinamacrocycles 6a ,b (top) and 6c,d (bottom).
yields. These were characterized analogously to the
other new compounds above.
3. Str u ctu r a l a n d Dyn a m ic P r op er ties. The crys-
tal structure of 6b has been reported previously,6c and
those of 6a ,c and the solvate 6d ‚(toluene)0.5 were
similarly determined as summarized in Table 1 and the
Experimental Section. The molecular structures of all
are depicted in Figure 2, which highlights the basket-
handle-like trans-spanning ligands. Key bond lengths,
bond angles, and torsion angles are listed in Table 2.
In the case of 6a , two independent molecules were
present in the unit cell. However, since the macrocycle
conformations were analogous, as indicated by the close
correspondence of the torsion angles in Table 2, only
one is shown in Figure 2.
F igu r e 3. View of 6c down the P-Pt-P axis highlighting
the C6H5/C6F5/C6H5 stacking interaction.
An alternative view of 6c is given in Figure 3. This
illustrates a stacking interaction involving the pen-
tafluorophenyl ligand and a phenyl group on each
phosphorus, which is common to all structures and
analyzed further below. The averages of the two cen-
troid-centroid distances in 6a -d were 3.91, 3.60, 3.73,
and 3.72 Å, respectively.
illustrated in Scheme 3.18 Said differently, the methyl-
ene chain of the trans-spanning phosphine must be able
to pass over the smaller chloride ligand. At room
temperature, this is fast on the NMR time scale for 6b-
d , but slow for 6a .
A toluene-d8 solution of 6a was gradually warmed to
1
95 °C, and 13C and H NMR spectra were periodically
The NMR properties of the 13-membered macrocycle
6a differed from those of 6b-d . The latter group gave
only a single set of PPh2 13C NMR resonances and
PCH2CH2 1H NMR resonances. However, 6a exhibited
two sets of signals (50:50). In principle, all geminal
phenyl groups and methylene protons are diastereotopic
in these compounds. However, they can be exchanged
by a 180° rotation of the Cl-Pt-C6F5 moiety, as
recorded. No coalescence or significant broadening of the
(18) The exchange of Ha and Hb in Scheme 3 can be analyzed as
follows. In both I and II, Ha and Hd are enantiotopic, as are Hb and
Hc. Ha is diastereotopic with Hb and Hc. Ha in I exchanges with Hc in
II, which is in turn chemical shift equivalent with enantiotopic Hb.
Similarly, Hb in I exchanges with Hd in II, which is in turn chemical
shift equivalent with enantiotopic Ha. The diastereotopic phenyl groups
exchange analogously.

Metallamacrocycles via Alkene Metatheses
Organometallics, Vol. 22, No. 26, 2003 5571
Ta ble 2. Key Bon d Len gth s, Bon d An gles, a n d Tor sion An gles
6a a
6b
6c
6d
Bond Lengths (Å)
Pt-P(1)
2.3054(11)/2.3066(11)
2.3100(11)/2.3235(11)
2.3742(10)/2.3595(10)
2.025(4)/2.005(4)
1.537(7)/1.526(7)
1.516(6)/1.514(7)
1.552(8)/1.418(8)
1.511(9)/1.547(8)
1.514(7)/1.473(7)
1.509(8)/1.522(8)
1.446(8)/1.571(7)
1.508(7)/1.527(8)
1.532(6)/1.520(7)
2.306(2)
2.299(2)
2.359(2)
1.996(7)
1.531(9)
1.505(9)
1.510(9)
1.488(9)
1.506(9)
1.529(11)
1.385(12)
1.458(13)
1.408(15)
1.425(15)
1.376(15)
1.475(10)
1.508(9)
2.2984(11)
2.2995(12)
2.3524(12)
2.008(4)
1.532(6)
1.506(6)
1.520(6)
1.530(6)
1.525(7)
1.505(7)
1.549(7)
1.510(8)
1.489(7)
1.531(7)
1.499(8)
1.507(7)
1.513(7)
1.527(7)
1.484(7)
1.520(7)
1.514(7)
2.3017(16)
2.3101(16)
2.3719(16)
2.016(6)
1.513(11)
1.517(9)
1.485(11)
1.526(12)
1.446(14)
1.516(14)
1.458(14)
1.472(14)
1.497(13)
1.514(14)
1.505(13)
1.483(13)
1.503(10)
1.514(9)
Pt-P(2)
Pt-Cl
Pt-C(41)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
C(7)-C(8)
C(8)-C(9)
C(9)-C(10)
C(10)-C(11)
C(11)-C(12)
C(12)-C(13)
C(13)-C(14)
C(14)-C(15)
C(15)-C(16)
C(16)-C(17)
C(17)-C(18)
C(18)-C(19)
C(19)-C(20)
1.495(9)
1.519(9)
1.536(11)
1.513(8)
1.522(10)
Bond Angles (deg)
C(41)-Pt-P(1)
C(41)-Pt-P(2)
P(1)-Pt-P(2)
C(41)-Pt-Cl
P(1)-Pt-Cl
90.43(11)/91.27(12)
92.80(11)/93.35(12)
176.25(4)/175.16(4)
177.55(12)/179.52(13)
88.52(4)/88.56(4)
91.7(2)
90.52(12)
92.22(12)
176.94(4)
177.04(12)
89.85(4)
91.54(17)
90.62(17)
174.26(6)
176.35(19)
88.91(6)
91.4(2)
172.00(7)
174.3(2)
88.67(7)
89.07(7)
P(2)-Pt-Cl
88.17(4)/86.84(7)
87.34(4)
89.28(6)
Torsion Angles (deg)
P(2)-Pt(1)-P(1)-C(1)
P(1)-Pt(1)-P(2)-C(n)b
Pt(1)-P(1)-C(1)-C(2)
P(1)-C(1)-C(2)-C(3)
18.4(6)/-26.84(6)
-33.1(6)/38.7(6)
44.2(3)/50.9(4)
-114.6(6)
126.8(6)
-46.3(6)
166.5(6)
-169.6(7)
177.6(7)
-174.7(7)
69.0(12)
-106.4(16)
178.6(12)
-163.1(17)
59(3)
65.6(8)
-119.4(6)
112.0(6)
-44.3(7)
175.6(7)
179.7(11)
-174.3(14)
-169(2)
176(2)
-75.8(8)
40.5(4)
-151.6(3)/155.4(3)
-176.1(4)/-178.9(4)
-58.0(6)/56.7(8)
-54.2(6)/54.7(8)
-171.1(4)/170.1(4)
-54.0(7)/52.3(7)
-55.4(7)/56.4(6)
-61.4(7)/64.4(7)
-169.6(3)
176.8(4)
-174.6(4)
172.0(4)
68.8(6)
C(1)-C(2)-C(3)-C(4)
C(2)-C(3)-C(4)-C(5)
C(3)-C(4)-C(5)-C(6)
C(4)-C(5)-C(6)-C(7)
C(5)-C(6)-C(7)-C(8)
173.6(4)
58.2(7)
61.0(7)
174(2)
C(6)-C(7)-C(8)-C(9)
44(3)
89(3)
-174.1(16)
85(2)
-160.8(17)
178.3(17)
-66.7(16)
176.3(9)
178.9(8)
168.4(7)
177.8(6)
175.0(6)
-167.9(5)
47.6(6)
C(7)-C(8)-C(9)-C(10)
C(8)-C(9)-C(10)-C(11)
C(9)-C(10)-C(11)-C(12)
C(10)-C(11)-C(12)-C(13)
C(11)-C(12)-C(13)-C(14)
C(12)-C(13)-C(14)-C(15)
C(13)-C(14)-C(15)-C(16)
C(14)-C(15)-C(16)-C(17)
C(15)-C(16)-C(17)-C(18)
C(16)-C(17)-C(18)-C(19)
C(17)-C(18)-C(19)-C(20)
C(n-2)-C(n-1)-C(n)-P(2)b
Pt(1)-P(2)-C(n)-C(n-1)b
-179.7(5)
-170.7(5)
-60.0(7)
-61.7(7)
178.6(5)
176.6(5)
178.5(5)
175.0(5)
84(3)
177.2(18)
-175.3(13)
176.1(4)/-176.2(4)
-50.2(4)/-47.3(4)
-163.7(7)
43.2(7)
168.3(4)
-53.9(4)
a
b
Two independent molecules are present in the unit cell. n ) number of methylene groups in the macrocycle.
Sch em e 3. Exch a n ge of Dia ster otop ic Gr ou p s in
Ma cr ocyclic Com p lexes
1
para-C6H5 13C or PCHH′CHH′ H signals were noted.
Application of the coalescence formula,19 using the ∆ν
value for the para carbons (155.2 Hz, 25 °C), allowed a
lower limit of 17.4 kcal/mol (95 °C) to be placed upon
the barrier for the dynamic process in Scheme 3. A
complementary series of low-temperature spectra were
recorded with a THF-d8 solution of the 17-membered
macrocycle 6b. Between -5 and -90 °C, no decoales-
cence or significant broadening of the PPh2 13C or
PCH2CH2 1H signals was observed. Application of the
coalescence formula, using the ∆ν value for the para
carbons of 6a , allowed an upper limit of 8.4 kcal/mol
(-90 °C) to be placed on the barrier for the dynamic
process in Scheme 3.
4. Effect of Gem in a l Dim eth yl Su bstitu en ts. As
noted in the Introduction, geminal dimethyl groups can
have a beneficial effect upon cyclization efficiency.9,10
Accordingly, when this project was still in the planning
stage and before any preliminary success, the synthesis
(19) Sandstro¨m, J . Dynamic NMR Spectroscopy; Academic Press:
New York, 1982. Calculations utilized eq 7.4 b.

5572 Organometallics, Vol. 22, No. 26, 2003
Bauer et al.
Sch em e 4. Syn th esis of a Mon op h osp h in e a n d P la tin a m a cr ocycles Con ta in in g Gem in a l Dim eth yl Gr ou p s
of a dimethyl derivative of phosphine ligand 2b was
undertaken.20 For obvious reasons, it was sought to
avoid neopentyl functionality or PCH2C(CH3)2 or (CH3)2-
CCH2CHdCH2 linkages. Thus, the synthesis of the
phosphine Ph2P(CH2)2C(CH3)2(CH2)3CHdCH2 (2e) shown
in Scheme 4 was developed.
11%). Hence, we suspect that the minor 31P NMR signal
of 5e represents some type of dimeric or oligomeric
byproduct, as opposed to a CdC geometric isomer. In
any event, the geminal dimethyl groups in 3e clearly
present no impediment to macrocyclization. However,
the analogous complex lacking dimethyl groups (3b) is
such a good substrate that no beneficial effect is
apparent.
5. Oth er Rea ction s. Additional experiments were
conducted to help interpret the preceding data. First,
many macrocyclizations of organic R,ω-dienes have been
conducted with both catalyst 4 and Grubbs’ “second-
generation” catalyst Ru(dCHPh)(H2IMes)(PCy3)(Cl)2 (7,
Figure 1).23 The latter sometimes gives markedly dif-
ferent distributions of intra- and intermolecular prod-
ucts24 and is more reactive toward endocyclic macrocy-
clic alkenes.25 Thus, CH2Cl2 solutions of 3a ,b,c (0.0025
M) and 7 (10 mol %; added in two portions) were
refluxed for ca. 4 h. The product distributions before and
after workup were very close to those obtained under
similar conditions with 4, as indicated by the bracketed
values in Scheme 2. Hence, the catalyst 7 has no
significant effect on the yield or fraction of major
product.
The symmetrical dibromide BrCH2CH2C(CH3)2CH2-
CH2Br (Scheme 4) is easily obtained in two steps from
commercial 3,3-dimethylglutaric acid.21 It could be
desymmetrized by a cross-coupling with BrMgCH2CHd
CH2 in the presence of catalytic quantities of Li2CuCl4.22
Distillation gave the monosubstitution product, bro-
moalkene Br(CH2)2C(CH3)2(CH2)3CHdCH2 (1e), in 40%
yield. Subsequent reaction with KPPh2 gave the target
phosphine 2e in 62-41% yields. These new compounds
were characterized analogously to the other bromides
and phosphines above. The 1H and 13C NMR spectra
showed intense singlets for the geminal dimethyl groups.
The reaction of 2e and platinum complex [Pt(µ-Cl)-
(C6F5)(S(CH2CH2-)2)]2 as described for the other phos-
phines above gave the bis(phosphine) complex trans-
(Cl)(C6F5)Pt(PPh2(CH2)2C(CH3)2(CH2)3CHdCH2)2 (3e)
in 63% yield. As shown in Scheme 4, reaction with
Grubbs’ catalyst 4 afforded, after workup, the expected
We next wondered whether macrocycles of the type
6 might be efficiently accessed without recourse to
alkene metathesis. Thus, the platinum starting material
macrocyclic metathesis product trans-(Cl)(C6F5)Pt(PPh2-
(CH2)2C(CH3)2(CH2)3CHdCH(CH2)3C(CH3)2(CH2)2PPh2)-
1
in Scheme 2, [Pt(µ-Cl)(C6F5)(S(CH2CH2-)2)]2, and the
(5e) in 78% yield. The H NMR spectrum suggested a
8a,26
88:12 ratio of E/Z CdC isomers. The 31P NMR spectrum
of the crude reaction mixture showed only two signals
in a 9:91 area ratio.
diphosphine Ph2P(CH2)14PPh2
were combined in a
NMR tube in CD2Cl2 (1:1 Pt/diphosphine ratio, ca. 0.018
M). A multitude of products formed, as assayed by NMR
and TLC. The 31P NMR spectrum allowed an upper limit
Hydrogenation as above gave the saturated macro-
cycle trans-(Cl)(C6F5)Pt(PPh2(CH2)2C(CH3)2(CH2)8C-
(23) (a) Scholl, M.; Trnka, T. M.; Morgan, J . P.; Grubbs, R. H.
Tetrahedron Lett. 1999, 40, 2247. (b) Scholl, M.; Ding, S.; Lee, C. W.;
Grubbs, R. H. Org. Lett. 1999, 1, 953. (c) H2IMes ) 1,3-dimesityl-4,5-
dihydroimidazol-2-ylidene.
(24) Fu¨rstner, A.; Thiel, O. R.; Ackermann, L. Org. Lett. 2001, 3,
449.
(CH3)2(CH2)2PPh2) (6e). However, in both the crude and
analytically pure product (66% and 54% yields, respec-
tively), a second minor 31P NMR signal was present (ca.
(25) One good recent example involves an alkene-containing crown
ether: Kilbinger, A. F. M.; Cantrill, S. J .; Waltman, A. W.; Day, M.
W.; Grubbs, R. H. Angew. Chem., Int. Ed. 2003, 42, 3281; Angew. Chem.
2003, 115, 3403.
(26) Mohr, W.; Horn, C. R.; Stahl, J .; Gladysz, J . A. Synthesis 2003,
1279.
(20) Bauer, E. B. Diploma Thesis, University of Erlangen-Nurem-
berg, 1999.
(21) Eilbracht, P.; Acker, P.; Totzauer, W. Chem Ber. 1983, 116, 238.
(22) (a) Tamura, M.; Kochi, J . Synthesis 1971, 303. (b) J ohnson, D.
K.; Donohoe, J .; Kang, J . Synth. Commun. 1994, 24, 1557.

Metallamacrocycles via Alkene Metatheses
Organometallics, Vol. 22, No. 26, 2003 5573
Sch em e 5. Oth er Releva n t Ma cr ocycliza tion s
simple substitution reaction. Still smaller rings are
likely to have significant strain energy, and such targets
are unlikely to be accessible by our methodology.
However, we are optimistic regarding larger metal-
lamacrocycles. Although the data in Scheme 2 suggest
that intramolecular metathesis becomes less efficient
for the 21- and 23-membered macrocycles 5c,d , reac-
tions at higher dilution, which might have ameliorated
this trend, were not conducted.
2. Ma cr ocycliza tion Efficien cy. The most impor-
tant question regarding this work is “why are these
macrocyclizations so successful”? Only modest amounts
of dimeric or oligomeric byproducts form, despite condi-
tions that are not particularly dilute (ca. 0.0025 M,
corresponding to ca. 160 mg of 3a -e in 70 mL of CH2-
Cl2). In certain macrocyclizations, some type of favorable
conformational factor can be identified. For example,
there is a well-established “geminal dialkyl effect” in
carbocycle synthesis.9,10 When two alkyl groups are
present on the same carbon atom, C-CR2-C-C seg-
ments with gauche conformations become energetically
more competitive with anti conformations. Chains of
atoms with exclusively anti conformations are incapable
of cyclization, and all carbocycles require a certain
number of C-C-C-C torsion angles in the range of
0-90°.
In related metallamacrocyclizations involving cis
ligands, it is possible to identify features reminiscent
of the geminal dialkyl effect. Consider the cis bis-
(phosphine) platinum complex 12 in Scheme 5C (bot-
tom).6c The phenyl groups in the M-PPh2-CH2-CH2
segments should, relative to compounds with M-PH2-
CH2-CH2 or M-CH2-CH2-CH2 segments, increase the
fraction of gauche conformations. As illustrated by the
sequence of Newman-type projections III (anti/anti), IV
(gauche/anti), and V (gauche/gauche) in Scheme 6A
(top), this should enhance the rate of macrocyclization.
The alternative gauche/gauche conformation VI should
also be favorable for macrocyclization. Accordingly, 13,
which features a 17-membered ring, is obtained in good
yield.
However, in substrates such as 3a -e, the pendant
alkenes must furthermore be directed on the same side
of the metal square plane. Some relevant conformations,
as viewed down the PtPPh2-CH2CH2 bond in the
direction of the Cl-Pt-C6F5 axis, are given in Scheme
6B (middle). At present, we see no special feature that
would favor reaction of the macrocyclization-prone
gauche/gauche conformation IX over the oligomeriza-
tion-prone gauche/gauche conformation X. Other con-
formations are possible (e.g., a 180° rotation about one
Pt-P bond will generate another series), but the conclu-
sion remains the same. Since no bonding interactions
are evident between the coordinatively unsaturated
platinum moieties and CdC linkages in 5a -e, we
believe it unlikely that the platinum somehow serves
as a template for macrocyclization.
of 15% to be placed upon the yield of 6b. Hence,
metathesis provides a singularly successful route to
such macrocycles.
Discu ssion
1. Scop e of Ma cr ocycliza tion s. Schemes 2 and 4
clearly establish that 13- to 23-membered macrocycles
can be accessed in high yields by ring-closing metathe-
ses of square-planar platinum complexes with trans-
disposed alkene-containing phosphines. As depicted in
Scheme 5A (top), the related square-planar rhodium
complex 8 reacts similarly to give the 17-membered
macrocycle 9.6a There is every reason to believe that
alkene-containing sulfur, nitrogen, and other donor
ligands, as well as other metals, can be analogously
employed.1
To our knowledge, the shortest conformationally
unconstrained trans-spanning diphosphorus donor ligand
is found in the platinum complex 10 (Scheme 5B,
middle).3,27,28 This 12-membered platinacycle was ob-
tained in low yield together with the dimer 11 by a
It is now well established that C6H5/C6F5 π interac-
tions are attractive and a driving force in many crystal-
lizations.29 These are evident in each of the crystal
(28) Other trans-spanning diphosphines that give 12-membered or
smaller metallacycles contain arene rings as part of the backbone.3
An early report of a nickel complex with a trans-spanning Cy2P(CH2)5-
PCy2 ligand has been questioned.3,27
(27) (a) Shaw, B. L. J . Am. Chem. Soc. 1975, 97, 3856. (b) Pryde,
A.; Shaw, B. L.; Weeks, B. J . Chem. Soc., Dalton. Trans. 1976, 322.

5574 Organometallics, Vol. 22, No. 26, 2003
Sch em e 6. Selected Con for m a tion a l Equ ilibr ia
Bauer et al.
structures of 6a -d (Figures 2, 3). Could they somehow
template the macrocyclizations? Since the rhodium
complex 8, which lacks a pentafluorophenyl ligand,
reacts similarly (Scheme 5A), such interactions are
definitely not required. Furthermore, consider the con-
formations XI and XII of 3a -e in Scheme 6C (bottom),
in which C6H5/C6F5/C6H5 π stacks are assumed. There
would seem to be a roughly equal energetic probability
for the pendant alkenes to be on opposite versus
identical sides of the platinum square plane. Thus, no
net bias for ring closure would result.
Regardless of the exact basis for the good yields of
our trans-spanning diphosphine complexes, Shaw has
provided strong support for the general importance of
phosphorus-based geminal-dialkyl effects.27 He studied
substitution reactions analogous to that in Scheme 5B
(middle), but with diphosphines with 10- and 12-
methylene chains. With bulky P(t-Bu)2 endgroups,
trans-spanning diphosphine complexes and dimers
thereof were the major products. Note that in Pt-P(t-
Bu)2-CH2-CH2 segments with anti conformations, the
methylene chain must occupy the interstice between the
two large tert-butyl groups. In contrast, anti conforma-
tions involving smaller PPh2 endgroups should be
energetically more accessible. Accordingly, analogous
reactions with the diphosphines Ph2P(CH2)nPPh2 (n )
9, 10, 12) led only to open-chain oligomeric species.
3. Oth er Str u ctu r a l a n d Dyn a m ic P r op er ties.
Additional structural features of 6a -d are relevant to
phenomena analyzed above. First, Table 2 shows that
all complexes generally have similar bond lengths and
angles about platinum. The angles involving the trans
ligands show the greatest variance. However, the
P-Pt-P bond angle in the smallest macrocycle 6a ,
which might have contracted if ring strain were signifi-
cant, was larger than those of 6b,d (176.25(4)°/175.16-
(4)° vs 172.00(7)° and 174.26(6)°).
Consider the torsion angle patterns of the macrocycles
next. All Pt-PPh2-CH2-CH2 segments (Pt(1)-P(1)-
C(1)-C(2) and Pt(1)-P(2)-C(n)-C(n-1)) exhibit gauche
conformations with torsion angles in the narrow range
of (40.5(4)° to (53.9(4)°. All PPh2-CH2-CH2-CH2
segments in turn exhibit anti conformations, with
torsion angles in the range of (151.6(3)° to (176.2(4)°.
The neighboring sequences of four carbon atoms also
show anti conformations, with the exception of C(7)-
C(8)-C(9)-C(10) in the smallest macrocycle 6a (torsion
angle -61.4(7)°/64.4(7)°). Complex 6a features a total
of five all-carbon gauche segments, as does 6c. However,
6b and 6c exhibit three and four, respectively. Natu-
rally, all of these macrocycles will have a distribution
of conformations in solution, and crystallization in
identical motifs is not to be expected.
(29) (a) Collings, J . C.; Roscoe, K. P.; Robins, E. G.; Batsanov, A. S.;
Stimson, L. M.; Howard, J . A. K.; Clark, S. J .; Marder, T. B. New J .
Chem. 2002, 26, 1740, and references therein. (b) Ponzini, F.; Zagha,
R.; Hardcastle, K.; Siegel, J . S. Angew. Chem., Int. Ed. 2000, 39, 2323;
Angew. Chem. 2000, 112, 2413. (c) Coates, G. W.; Dunn, A. R.; Henling,
L. M.; Ziller, J . W.; Lobkovsky, E. B.; Grubbs, R. H. J . Am. Chem. Soc.
1998, 120, 3641. (d) Renak, M. L.; Bartholomew, G. P.; Wang, S.;
Ricatto, P. J .; Lachicotte, R. J .; Bazan, G. C. J . Am. Chem. Soc. 1999,
121, 7787.
Shaw and Mason have reported the crystal structures
of an Ir(CO)(Cl) adduct of the trans-spanning diphos-
phine (t-Bu)2P(CH2)10P(t-Bu)2 and a Pt(Cl)2 adduct of

Metallamacrocycles via Alkene Metatheses
Organometallics, Vol. 22, No. 26, 2003 5575
the longer diphosphine (t-Bu)2P(CH2)12P(t-Bu)2.30 These
13- and 15-membered macrocycles exhibit torsion angle
patterns for the six-atom M-PR2-CH2-CH2-CH2-
CH2 segments analogous to those of 6b-d . They feature
three and four all-carbon gauche segments, respectively.
When 6a -d are viewed with atoms at van der Waals
radii, the macrocycles contain little “void space”. None-
theless, passage of the chloride ligand through the
macrocycle, as shown for a Pt-X moiety in Scheme 3, is
rapid on the NMR time scale for 6b-d . Steric interac-
tions in these dynamic processes can be analyzed as
follows. First, the distances from platinum to the
furthest of the two most remote carbons (e.g., C(5) and
C(6) in 6a ) in each macrocycle are calculated (6a , 5.62
Å; 6b, 7.83 Å; 6c, 10.22 Å; 6d , 11.44 Å). The van der
Waals radius of an sp3 carbon (1.70 Å)31 is then
subtracted (6a , 3.92 Å; 6b, 6.13 Å; 6c, 8.52 Å; 6d , 9.74
Å). These values are compared to the sum of the
platinum-chlorine bond distance (ca. 2.36 Å) plus the
van der Waals radius of chlorine (1.78 Å),31 or 4.14 Å.
Hence, even without taking into account the methyl-
ene hydrogen atoms (van der Waals radius 1.20 Å), it
is readily apparent that there will be substantial steric
interactions for such a process with 6a (4.14 Å “vehicle
height” vs 3.92 Å “bridge height”). Accordingly, the
barrier could not be measured by NMR and is at least
17.4 kcal/mol at 95 °C. Given the more generous spacing
in 6b (4.14 vs 6.13 Å), the much lower barrier, less than
8.4 kcal/mol at -90 °C, is easy to rationalize. However,
since the coalescence or decalescence of diastereotopic
groups could not be observed, it has not been possible
to measure an exact barrier. For this purpose, an
analogous 15-membered macrocycle should be ideal.
4. P r osp ective. This work has significantly advanced
the application of alkene metathesis to the synthesis of
topologically novel inorganic and organometallic sys-
tems. As noted above, the extension of Schemes 2 and
4 to the preparation of a variety of other adducts of
trans-spanning ligands can be anticipated. Further-
more, alkyne metathesis has recently been employed to
convert an analogue of 3b with carbon-carbon triple
bonds to a platinamacrocycle.32 This avoids the compli-
cation of E/Z CdC isomers. Finally, novel macrocycliza-
tions involving more complex eductsssuch as when the
trans phosphorus or other donor atoms contain two
(CH2)nCHdCH2 moietiesswill be described in upcoming
full papers.6b,33
rich), KPPh2 (Fluka, 0.5 M in THF), Ru(dCHPh)(PCy3)2(Cl)2
(4, Strem), Ru(dCHPh)(H2IMes)(PCy3)(Cl)2 (7, Strem),23c Pd/C
(10%, Lancaster or Acros), and BrMgCH2CHdCH2 (1 M in
ether, Fluka), used as received. All Li2CuCl4 solutions were
freshly generated from LiCl (0.424 g, 10.00 mmol), CuCl2
(0.673 g, 5.00 mmol), and THF (50 mL).22 NMR spectra were
obtained on Bruker or J EOL 400 MHz spectrometers. IR and
mass spectra were recorded on ASI React-IR 1000 and Micro-
mass Zabspec instruments, respectively. DSC and TGA data
were obtained with a Mettler-Toledo DSC-821 instrument.34
Microanalyses were conducted on
instrument.
a Carlo Erba EA1110
Br (CH2)8CHdCH2 (1c).11 A Schlenk flask was charged with
HO(CH2)8CHdCH2 (2.000 g, 12.8 mmol), CBr4 (4.788 g, 14.4
mmol), and CH2Cl2 (20 mL) and cooled to 0 °C. Over the course
of 20 min, PPh3 (4.510 g, 17.2 mmol) was added in portions.
The mixture was stirred for 2 h at 0 °C. After ca. 30 min, a
white precipitate formed. The mixture was stirred for 22 h at
room temperature. The solvent was removed by rotary evapo-
ration and oil pump vacuum. The residue was suspended in
hexane (5 mL) and the mixture filtered through silica gel (5
× 2.5 cm column; rinsed with 1:1 v/v CH2Cl2/hexanes). The
solvent was removed from the filtrate by rotary evaporation,
and distillation (9 × 10-3 mbar, 58 °C) gave 1c as a colorless
oil (2.084 g, 9.597 mmol, 75%). NMR (δ, CDCl3): 1H 5.86-
5.79 (m, 1 H, CHd), 5.04-4.94 (m, 2 H, dCH2), 3.44-3.40 (t,
3J HH ) 8.7, 2 H, BrCH2), 2.07-2.04 (m, 2 H, CH2CHd), 1.91-
1.83 (m, 2 H, BrCH2CH2), 1.46-1.32 (m, 10 H, 5CH2); 13C-
{1H} 139.5 (s, CHd), 114.6 (s, dCH2), 34.4 (s, CH2), 34.2 (s,
CH2), 33.2 (s, CH2), 29.7 (s, CH2), 29.4 (s, CH2), 29.3 (s, CH2),
29.1 (s, CH2), 28.5 (s, CH2).
P P h 2(CH2)4CHdCH2 (2a ). A Schlenk flask was charged
with 1a (0.500 g, 3.066 mmol) and THF (7 mL) and cooled to
0 °C. Then KPPh2 (0.5 M in THF, 6.1 mL, 3.1 mmol) was added
dropwise with stirring to the colorless solution over 20 min.35
A white precipitate formed. The mixture was stirred for 1 h
at 0 °C and 1 h at room temperature. The solvent was removed
by oil pump vacuum and the residue suspended in CH2Cl2 (5
mL). The suspension was chromatographed on silica gel (5 ×
2.5 cm column; eluted with 1:1 v/v CH2Cl2/hexanes). The
solvent was removed from the product fraction by rotary
evaporation and oil pump vacuum to give 2a as a viscous
cloudy liquid (0.345 g, 1.282 mmol, 41%). Anal. Calcd for
C
18H21P: C, 80.57; H 7.89. Found: C, 80.35; H, 7.89. NMR (δ,
CDCl3): 1H 7.49-7.45 (m, 4 H of 2Ph), 7.37-7.36 (m, 6 H of
2Ph), 5.86-5.79 (m, 1 H, CHd), 5.05-4.96 (m, 2 H, dCH2),
2.12-2.07 (m, 4 H, CH2CHd + PCH2), 1.61-1.48 (m, 4 H,
2CH2); 13C{1H} 138.9 (d, J CP ) 13.1, i-Ph),36 138.6 (s, CHd),
1
132.6 (d, J CP ) 18.3, o-Ph),36 128.4 (s, p-Ph),36 128.3 (d, J CP
2
3
) 6.6, m-Ph),36 114.5 (s, dCH2), 33.3 (s, CH2CHd), 30.4 (d,
3J CP ) 13.0, PCH2CH2CH2),37 27.9 (d, J CP ) 11.4, PCH2),37
1
25.4 (d, J CP ) 16.2, PCH2CH2);37 31P{1H} -15.5 (s). IR (cm-1
,
2
oil film): 3057, 2926, 2864, 1436, 1177, 1119, 1069, 718, 695.
MS:38 269 (2a +, 100%).
Exp er im en ta l Section
P P h 2(CH2)6CHdCH2 (2b).6c,12 Anal. Calcd for C20H25
P
(viscous liquid, 74%): C, 81.05; H, 8.50. Found: C, 79.91; H,
8.44. NMR (δ, CDCl3): 1H 7.45-7.32 (m, 10 H of 2Ph), 5.79
(m, 1 H, CHd), 5.02-4.91 (m, 2 H, dCH2), 2.07-1.99 (m, 4 H,
Gen er a l Da ta . All reactions were conducted under N2 (or
H2) atmospheres. Chemicals were treated as follows: THF,
distilled from Na/benzophenone; CH2Cl2, distilled from CaH2
for reactions or simple distillation for chromatography; hex-
anes and ethanol, simple distillation; acetic acid, ClCH2CH2-
Cl (99%, Fluka), CDCl3, C6D6, toluene-d8, THF-d8, Br(CH2)4-
CHdCH2 (1a; 97%, Fluka), Br(CH2)6CHdCH2 (1b; 97%, Aldrich
or Fluka), HO(CH2)8CHdCH2 (97%, Fluka), CBr4 (98%, Lan-
caster), PPh3 (99%, Acros), Br(CH2)9CHdCH2 (1d , 97% Ald-
(34) Cammenga, H. K.; Epple, M. Angew. Chem. 1995, 107, 1284;
Angew. Chem., Int. Ed. Engl. 1995, 34, 1171.
(35) The addition of the red KPPh2 solution was continued until
some color began to persist.
(36) The PC6H5 13C NMR signals were assigned as described by:
Mann, B. E. J . Chem. Soc., Perkin Trans. 2 1972, 30. The resonance
with the chemical shift closest to benzene was attributed to the meta
carbon, and the least intense phosphorus-coupled resonance was
attributed to the ipso carbon.
(30) March, F. C.; Mason, R.; Thomas, K. M.; Shaw, B. L. J . Chem.
Soc., Chem. Commun. 1975, 584.
(31) Bondi, A. J . Phys. Chem. 1964, 68, 441.
(32) Bauer, E. B.; Szafert, S.; Hampel, F.; Gladysz, J . A. Organo-
metallics 2003, 22, 2184.
(37) The PCH2CH2CH2 13C NMR signals were assigned by analogy
to chemical shift and coupling constant trends established (by COSY
and INADEQUATE pulse sequences) for other compounds with Ar2P-
(CH2)6X linkages.8a,26
(33) Shima, T.; Bauer, E. B.; Hampel, F.; Gladysz, J . A. Manuscript
in preparation.
(38) m/z (FAB, 3-NBA) for most intense peak of isotope envelope
(relative intensity, %).

5576 Organometallics, Vol. 22, No. 26, 2003
Bauer et al.
CH2CHd + PCH2), 1.45-1.27 (m, 8 H, 4CH2); 13C{1H} 139.0
(d, 1J CP ) 14.7, i-Ph),36 138.98 (s, CHd), 132.7 (d, 2J CP ) 18.3,
(virtual t,40 J CP ) 5.1, m-Ph),41 114.1 (s, dCH2), 33.3 (s, CH2-
CHd), 30.5 (virtual t,40 J CP ) 7.7, PCH2CH2CH2),42 25.8
(virtual t,40 J CP ) 17.2, PCH2),42 25.0 (s, PCH2CH2);42 31P{1H}
3
o-Ph),36 128.3 (d, J CP ) 4.5, m-Ph),36 128.2 (s, p-Ph),36 114.2
3
1
(s, dCH2), 33.6 (s, CH2CHd), 31.0 (d, J CP ) 13.7, PCH2-
16.5 (s, J PPt ) 2661).43 IR (cm-1, oil film): 3080, 3061, 2930,
CH2CH2),37 28.0 (br s, double intensity, CH2CH2CH2CHd), 28.0
(d, 1J CP ) 10.7, PCH2),37 25.7 (d, 2J CP ) 15.3, PCH2CH2);37 31P-
{1H} -15.8 (s). IR (cm-1, oil film): 3073, 2927, 2855, 1481,
1462, 1434, 1096, 1026, 912, 740, 696. MS:38 297 (2b+, 100%).
2860, 1502, 1463, 1436, 1104, 1061, 957, 907, 807, 737, 691.
MS:38 933 (3a +, 5%), 898 ([3a - Cl]+, 95%), 730 ([3a - Cl -
C6F5]+, 30%), 461 ([3a - Cl - C6F5 - Ph2PR]+, 40%), 268 (Ph2-
PR+, 100%).
tr a n s-(Cl)(C6F 5)P t(P P h 2(CH2)6CHdCH2)2 (3b).6c,12 Anal.
Calcd for C46H50ClF5P2Pt (colorless oil, 71-79%): C, 55.79; H,
5.09. Found: C, 55.87; H, 5.17. NMR (δ, CDCl3): 1H 7.50-
7.46 (m, 8 H of 4Ph), 7.32-7.22 (m, 12 H of 4Ph), 5.84-5.74
(m, 2 H, 2CHd), 5.01-4.90 (m, 4 H, 2 dCH2), 2.60-2.54 (m,
4 H, 2PCH2), 2.05-2.00 (m, 4 H, 2CH2CHd), 1.97-1.85 (m, 4
H, 2PCH2CH2), 1.44-1.30 (m, 12 H, 6CH2); 13C{1H}39 138.9
(s, CHd), 133.0 (virtual t,40 J CP ) 5.5, o-Ph),41 130.8 (virtual
t,40 J CP ) 27.6, i-Ph),41 130.2 (s, p-Ph),41 128.0 (virtual t,40 J CP
) 5.5, m-Ph),41 114.3 (s, dCH2), 33.8 (s, CH2CHd), 31.3 (virtual
t,40 J CP ) 7.4, PCH2CH2CH2),42 28.8, (s, double intensity, CH2),
26.0 (virtual t,40 J CP ) 16.5, PCH2),42 25.6 (s, PCH2CH2);42 31P-
P P h 2(CH2)8CHdCH2 (2c). A Schlenk flask was charged
with 1c (1.000 g, 4.605 mmol) and THF (22 mL) and cooled to
0 °C. Then KPPh2 (0.5 M in THF, 9.2 mL, 4.6 mmol) was added
dropwise with stirring to the colorless solution over 20 min.35
A white precipitate formed. The mixture was stirred for 0.5 h
at 0 °C and 1 h at room temperature. The solvent was removed
by oil pump vacuum and the residue suspended in CH2Cl2 (5
mL). The suspension was filtered through neutral alumina (5
× 2.5 cm column, rinsed with 1:1 v/v CH2Cl2/hexanes). The
solvent was removed from the filtrate by rotary evaporation
and oil pump vacuum to give 2c as a viscous cloudy liquid
(1.422 g, 4.383 mmol, 95%). Anal. Calcd for C22H29P: C, 81.45;
H, 9.01. Found: C, 81.11; H, 8.93. NMR (δ, CDCl3): 1H 7.44-
7.42 (m, 10 H of 2Ph), 5.85-5.82 (m, 1 H, CHd), 5.05-4.95
(m, 2 H, dCH2), 2.10-2.03 (m, 4 H, CH2CHd + PCH2), 1.46-
1
{1H} 16.6 (s, J PPt ) 2659).43 IR (cm-1, oil film): 3080, 2930,
2856, 1502, 1463, 1436, 1104, 1061, 1000, 953, 911, 803, 741,
690. MS:38 989 (3b+, 3%), 954 ([3b - Cl]+, 30%), 785 ([3b - Cl
- C6F5]+, 20%), 489 ([Pt(Ph2P(CH2)6CHdCH2)]+, 80%), 297
([Ph2P(CH2)6CHdCH2]+, 100%).
1.29 (m, 12 H, 6CH2); 13C{1H} 139.6 (s, CHd), 139.0 (d, 1J CP
)
2
13.0, i-Ph),36 132.7 (d, J CP ) 18.3, o-Ph),36 128.6 (s, p-Ph),36
3
128.3 (d, J CP ) 6.6, m-Ph),36 114.5 (s, dCH2), 34.2 (s, CH2-
tr a n s-(Cl)(C6F 5)P t(P P h 2(CH2)8CHdCH2)2 (3c). A Schlenk
flask was charged with [Pt(µ-Cl)(C6F5)(S(CH2CH2-)2)]2 (0.304
g, 0.313 mmol),14 2c (0.406 g, 1.252 mmol), and CH2Cl2 (16
mL). The mixture was stirred (11 h), and the solvent was
removed by oil pump vacuum. The residue was chromato-
graphed on neutral alumina (14 × 2.5 cm column) using CH2-
Cl2/hexanes (1:1 v/v). The solvent was removed from the
product fraction by rotary evaporation and oil pump vacuum
to yield 3c as a colorless oil (0.425 g, 0.406 mmol, 65%), which
solidified upon storage to a white powder. Anal. Calcd for
CHd), 31.6 (d, 3J CP ) 13.0, PCH2CH2CH2),37 29.8 (s, CH2), 29.6
1
(s, CH2), 29.5 (s, CH2), 29.3 (s, CH2), 28.5 (d, J CP ) 11.7,
2
PCH2),37 26.4 (d, J CP ) 15.8, PCH2CH2);37 31P{1H} -14.8 (s).
IR (cm-1, oil film): 2922, 2853, 1440, 1181, 1119, 1073, 996,
783, 748, 718, 695. MS:38 341 ([2cdO]+, 60%), 325 (2c+, 100%).
P P h 2(CH2)9CHdCH2 (2d ).13 A Schlenk flask was charged
with 1d (2.500 g, 10.72 mmol) and THF (50 mL). Then KPPh2
(0.5 M in THF, 21.4 mL, 10.7 mmol) was added dropwise with
stirring.35 After 1 h, the solvent was removed by oil pump
vacuum. Then CH2Cl2 was added, and the mixture was filtered
through silica gel (5 × 2.5 cm column, rinsed with CH2Cl2).
The solvent was removed from the filtrate by rotary evapora-
tion, and the residue distilled under reduced pressure to give
2d as a colorless liquid (3.287 g, 9.71 mmol, 91%). NMR (δ,
CDCl3): 1H 7.42 (m, 4 H of 2Ph), 7.32 (m, 6 H of 2Ph), 5.81
(m, 1 H, CHd), 4.92 (m, 2 H, dCH2), 2.03 (m, 4 H, CH2CHd
+ PCH2), 1.44 (m, 2 H, PCH2CH2), 1.37 (m, 2H, PCH2CH2CH2),
C
50H58ClF5P2Pt: C, 57.39; H, 5.59. Found: C, 57.42; H, 5.39.
NMR (δ, CDCl3): 1H 7.54-7.51 (m, 8 H of 4Ph), 7.36-7.26
(m, 12 H of 4Ph), 5.87-5.80 (m, 2 H, 2CHd), 5.05-4.97 (m, 4
H, 2 dCH2), 2.63-2.59 (m, 4 H, 2PCH2), 2.07-2.04 (m, 4 H,
2CH2CHd), 1.94-1.90 (m, 4 H, 2PCH2CH2), 1.46-1.32 (m, 20
H, 10CH2); 13C{1H}39 139.2 (s, CHd), 133.0 (virtual t,40 J CP
)
5.8, o-Ph),41 130.9 (virtual t,40 J CP ) 27.4, i-Ph),41 130.2 (s,
p-Ph),41 127.9 (virtual t,40 J CP ) 5.1, m-Ph),41 114.1 (s, dCH2),
33.8 (s, CH2CHd), 31.4 (virtual t,40 J CP ) 7.5, PCH2CH2CH2),42
29.3 (s, CH2), 29.2 (s, CH2), 29.1 (s, CH2), 28.9 (s, CH2), 26.0
(virtual t,40 J CP ) 17.4, PCH2),42 25.6 (s, PCH2CH2);42 31P{1H}
1.27 (m, 10 H, 5CH2); 13C{1H} 139.2 (s, CHd), 139.0 (d, 1J CP
)
)
2
3
14.7, i-Ph),36 132.6 (d, J CP ) 18.3, o-Ph),36 128.4 (d, J CP
4.5, m-Ph),36 128.3 (s, p-Ph),36 114.1 (s, dCH2), 33.7 (s, CH2-
17.3 (s, J PPt ) 2659).43 IR (cm-1, powder film): 3076, 2934,
1
3
CHd), 31.2 (d, J CP ) 13.7, PCH2CH2CH2),37 29.4 (s, double
2856, 1498, 1459, 1436, 1104, 1058, 996, 953, 907, 803, 741,
695. MS:38 1046 (3c+, 1%), 1010 ([3c - Cl]+, 100%), 842 ([3c
- Cl - C6F5]+, 40%), 515 ([Pt(Ph2P(CH2)6CHdCH2)]+, 95%).
tr a n s-(Cl)(C6F 5)P t(P P h 2(CH2)9CHdCH2)2 (3d ). Complex
[Pt(µ-Cl)(C6F5)(S(CH2CH2-)2)]2 (0.147 g, 0.151 mmol),14 2d
(0.406 g, 1.252 mmol), and CH2Cl2 (8 mL) were combined in a
procedure analogous to that for 3c. An identical workup gave
3d as a colorless oil (0.180 g, 0.168 mmol, 55%), which became
a wax upon storage. Anal. Calcd for C52H62ClF5P2Pt: C, 58.13;
H, 5.82. Found: C, 57.84; H, 5.40. NMR (δ, CDCl3): 1H 7.56-
7.53 (m, 8 H of 4Ph), 7.36-7.27 (m, 12 H of 4Ph), 5.88-5.81
(m, 2 H, 2CHd), 5.06-4.95 (m, 4 H, 2 dCH2), 2.66-2.60 (m,
4 H, 2PCH2), 2.10-2.05 (m, 4 H, 2CH2CHd), 1.95-1.92 (m, 4
intensity, CH2), 29.2 (s, CH2), 29.1 (s, CH2), 28.9 (s, CH2), 28.0
(d, 1J CP ) 10.7, PCH2),37 25.9 (d, 2J CP ) 15.3, PCH2CH2);37 31P-
{1H} -15.3 (s). IR (cm-1, oil film): 3073, 2926, 2853, 1640,
1482, 1459, 1436, 911, 737, 695. MS:38 339 (2d , 100%).
tr a n s-(Cl)(C6F5)P t(P P h 2(CH2)4CHdCH2)2 (3a). A Schlenk
flask was charged with [Pt(µ-Cl)(C6F5)(S(CH2CH2-)2)]2 (0.200
g, 0.206 mmol),14 2a (0.222 g, 0.823 mmol), and CH2Cl2 (12
mL). The mixture was stirred (16 h), and the solvent was
removed by oil pump vacuum. The residue was chromato-
graphed on neutral alumina (10 × 2.5 cm column) using CH2-
Cl2/hexanes (1:1 v/v). The solvent was removed from the
product fraction by oil pump vacuum to yield 3a as a colorless
oil (0.205 g, 0.219 mmol, 54%). Anal. Calcd for C42H42ClF5P2-
Pt: C, 54.00; H, 4.53. Found: C, 53.66; H, 4.47. NMR (δ,
CDCl3): 1H 7.55-7.52 (m, 8 H of 4Ph), 7.37-7.27 (m, 12 H of
4Ph), 5.86-5.80 (m, 2 H, 2CHd), 5.08-4.98 (m, 4 H, 2 dCH2),
2.67-2.61 (m, 4 H, 2PCH2), 2.16-2.11 (m, 4 H, 2CH2CHd),
2.01-1.94 (m, 4 H, 2PCH2CH2), 1.61-1.55 (m, 4 H, 2CH2); 13C-
{1H}39 138.3 (s, CHd), 133.0 (virtual t,40 J CP ) 5.8, o-Ph),41
130.7 (virtual t,40 J CP ) 27.4, i-Ph),41 130.3 (s, p-Ph),41 128.0
(40) Pregosin, P. S.; Venanzi, L. M. Chem. Brit. 1978, 276. The
apparent coupling between adjacent peaks of the triplet is given.
(41) The PtPC6H5 13C NMR assignments have abundant precedent.
See for example: J olly, P. W.; Mynott, R. Adv. Organomet. Chem. 1981,
19, 1981.
(42) Complexes with PtPCH2CH2CH2 linkages exhibit characteristic
13C NMR chemical shift and coupling constant patterns. For two
compounds, 3b in this work and a related species in ref 8a, the
assignments were confirmed by 1H,13C COSY spectra. The requisite
1H assignments were verified by 1H,1H COSY spectra.
(43) This coupling represents a satellite (d; 195Pt ) 33.8%) and is
not reflected in the peak multiplicity given.
(39) The C6F5 carbon resonances were not observed. These require
larger numbers of transients due to the fluorine and platinum
couplings.

Metallamacrocycles via Alkene Metatheses
Organometallics, Vol. 22, No. 26, 2003 5577
H, 2PCH2CH2), 1.46-1.32 (m, 24 H, 12CH2); 13C{1H}39 139.2
(s, CHd), 133.0 (virtual t,40 J CP ) 5.8, o-Ph),41 130.9 (virtual
t,40 J CP ) 27.4, i-Ph),41 130.2 (s, p-Ph),41 127.9 (virtual t,40 J CP
) 5.1, m-Ph),41 114.1 (s, dCH2), 33.8 (s, CH2CHd), 31.4 (virtual
t,40 J CP ) 7.5, PCH2CH2CH2),42 29.4 (s, double intensity, 2CH2),
a condenser. The solution was refluxed. After 2 h, the remain-
ing 4 was added. After 2 h, the solvent was removed by rotary
evaporation and oil pump vacuum. 31P{1H} NMR of residue
1
(δ, CDCl3): 17.8 (s, 4%) 17.2 (s, J PPt ) 2678,43 67%), 16.8 (s,
1J PPt ) 2679,43 14%), 16.7 (s, 4%), 16.5 (s, 1J PPt ) 2658,43 11%).
Then CH2Cl2 was added, and the mixture was filtered through
neutral alumina (5 × 2.5 cm column; rinsed with CH2Cl2). The
solvent was removed from the filtrate by rotary evaporation
and oil pump vacuum to give 5c as a pale pink solid (0.131 g,
0.129 mmol, 90%; E/Z ca. 80:20). Anal. Calcd for C48H50ClF5P2-
Pt: C, 56.84; H, 4.97. Found: C, 56.96; H, 5.10. NMR (δ): 1H
(CDCl3) 7.51-7.49 (m, 8 H of 4Ph), 7.33-7.24 (m, 12 H of 4Ph),
5.41-5.31 (m, 2 H, CHdCH), 2.70-2.65 (m, 4 H, 2PCH2),
2.29-2.26 (m, 4 H, 2CH2CHd), 2.06-2.05 (m, 4 H, 2PCH2CH2),
1.57-1.53 (m, 4 H, 2PCH2CH2CH2), 1.46-1.28 (m, 16 H, 8CH2)
and (C6D6) 7.63-7.54 (m, 8 H of 4Ph), 6.96-6.91 (m, 12 H of
4Ph), 5.52-5.47/5.43-5.38 (2 m, CHdCH, Z/E ca. 20:80 (see
text)), 2.67-2.58 (m, 4 H, 2PCH2), 2.41 (m, 4 H, 2CH2CHd),
2.14-2.10 (m, 4 H, 2PCH2CH2), 1.45-1.25 (m, 20 H, 10CH2);
13C{1H}39 (CDCl3) 132.7 (virtual t,40 J CP ) 5.8, o-Ph),41 131.7
(virtual t,40 J CP ) 27.2, i-Ph),41 131.0 (s, CHdCH), 130.1
(s, p-Ph),41 128.0 (virtual t,40 J CP ) 5.1, m-Ph),41 32.1 (s, CH2-
CHd), 31.9 (virtual t,40 J CP ) 8.0, PCH2CH2CH2),42 30.1 (s,
CH2), 29.7 (s, CH2), 28.9 (s, CH2), 28.4 (s, CH2), 26.9 (s, CH2),
26.7 (virtual t,40 J CP ) 17.6, PCH2);42 31P{1H}44 (CDCl3) 17.8
29.2 (s, CH2), 29.1 (s, CH2), 28.9 (s, CH2), 26.0 (virtual t,40 J CP
1
) 17.0, PCH2),42 25.6 (s, PCH2CH2);42 31P{1H} 17.3 (s, J PPt
)
2659).43 IR (cm-1, powder film): 3076, 2926, 2853, 1502, 1463,
1436, 1104, 1058, 996, 957, 919, 803, 737, 691. MS:38 1073 (3d +,
5%), 1038 ([3d - Cl]+, 100%), 870 ([3d - Cl - C6F5]+, 30%).
tr a n s-(Cl)(C6F5)P t(P P h 2(CH2)4CHdCH(CH2)4P P h 2) (5a).
A two-necked flask was charged with 3a (0.160 g, 0.171 mmol),
Grubbs’ catalyst 4 (ca. half of 0.007 g, 0.0086 mmol, 5 mol %),
and CH2Cl2 (72 mL; the resulting solution is 0.0024 M in 3a )
and fitted with a condenser. The solution was refluxed. After
2.5 h, the remaining 4 was added. After 2.5 h, the solvent was
removed by rotary evaporation and oil pump vacuum. 31P{1H}
NMR of residue (δ, CDCl3): 19.8 (s, 1J PPt ) 2692,43 84%), 19.3
(s, 3%), 18.2 (s, 6%), 17.3 (s, 4%), 17.0 (s, 3%). Then CH2Cl2
was added, and the mixture was filtered through neutral
alumina (5 × 2.5 cm column; rinsed with CH2Cl2). The solvent
was removed from the filtrate by rotary evaporation and oil
pump vacuum to give 5a as a white powder (0.147 g, 0.162
mmol, 95%; E/Z 90:10). Anal. Calcd for C40H38ClF5P2Pt: C,
53.02; H, 4.23. Found: C, 52.92; H, 4.35. NMR (δ, CDCl3): 1H
8.05-8.03 (m, 4 H of 4Ph), 7.52-7.28 (m, 6 H of 4Ph), 7.13-
6.92 (m, 10 H of 4Ph), 5.56-5.54/5.48-5.45 (m, 2 H, CHdCH,
E/Z 90:10 (see text)), 2.80-2.74 (m, 4 H, 2CH2), 2.52-2.50 (m,
2 H, CH2), 2.31-2.28 (m, 2 H, CH2), 2.15-2.13, 2.05-2.03 (2
m, 4 H, 2CH2CHd, tentative), 1.73-1.46 (m, 4 H, 2CH2); 13C-
{1H}39 134.7 (virtual t,40 J CP ) 6.6, o-Ph),41 132.5 (virtual t,40
J CP ) 26.5, i-Ph),41 131.5 (virtual t,40 J CP ) 28.5, i-Ph′),41 131.0
(s, p-Ph),41 130.9 (s, CHdCH), 130.4 (virtual t,40 J CP ) 5.1,
m-Ph),41 129.3 (s, p-Ph′),41 128.5 (virtual t,40 J CP ) 5.6, o-Ph′),41
127.5 (virtual t,40 J CP ) 4.6, m-Ph′),41 31.7 (s, CH2CHd), 30.9
1
1
(s, 4%) 17.2 (s, J PPt ) 2678,43 67%), 16.8 (s, J PPt ) 2679,43
14%), 16.7 (s, 4%), 16.5 (s, J PPt ) 2658,43 11%). IR (cm-1
,
1
powder film): 2926, 2853, 1502, 1463, 1436, 1104, 1058, 957,
803, 737, 695. MS:38 1017 (5c+, 3%), 982 ([5c - Cl]+, 100%),
813 ([5c - Cl - C6F5]+, 45%).
tr a n s-(Cl)(C6F5)P t(P P h 2(CH2)9CHdCH(CH2)9P P h 2) (5d).
A two-necked flask was charged with CH2Cl2 (66 mL), Grubbs’
catalyst 4 (ca. half of 0.009 g, 0.011 mmol, 7 mol %), and 3d
(0.170 g, 0.158 mmol) and fitted with a condenser. The solution
was refluxed. After 2 h, the remaining 4 was added. After 2
(virtual t,40 J CP ) 8.6, PCH2CH2CH2),42 27.0 (virtual t,40 J CP
)
)
h, the solvent was removed by rotary evaporation and oil pump
1
vacuum. 31P{1H} NMR of residue (δ, CDCl3): 17.6 (s, J PPt
)
)
1
17.5, PCH2),42 25.8 (s, PCH2CH2);42 31P{1H}44 19.8 (s, J PPt
1
2675,43 26%), 17.53 (s, < 2%), 17.5 (s, 10%), 17.4 (s, J PPt
1
2692,43 80%), 19.3 (s, 3%), 18.2 (s, J PPt ) 2693,43 10%), 17.3
(s, 5%), 17.0 (s, 2%). IR (cm-1, powder film): 2918, 2853, 1502,
1463, 1436, 1104, 1058, 957, 803, 737, 691. MS:38 905 (5a +,
< 5%), 870 ([5a - Cl]+, 100%), 702 ([5a - Cl - C6F5]+, 25%).
2670,43 48%), 17.2 (s, 16%). Then CH2Cl2 was added, and the
mixture was filtered through neutral alumina (5 × 2.5 cm
column; rinsed with CH2Cl2). The solvent was removed from
the filtrate by rotary evaporation and oil pump vacuum to give
5d as a pale pink solid (0.140 g, 0.134 mmol, 85%). Anal. Calcd
for C50H58ClF5P2Pt: C, 57.39; H, 5.59. Found: C, 55.62; H,
5.73.45 NMR (δ, CDCl3): 1H 7.48-7.45 (m, 8 H of 4Ph), 7.25-
7.21 (m, 12 H of 4Ph), 5.38-5.27 (m, 2 H, CHdCH), 2.63-
2.56 (m, 4 H, 2PCH2), 2.20-2.15 (m, ca. 1.3 H of 2 PCH2CH2),
2.07-1.99 (m, ca. 2.7 H of PCH2CH2 + 4 H of 2CH2CHd),
1.49-1.28 (m, 24 H, 12CH2); 13C{1H}39 132.8 (virtual t,40 J CP
) 5.8, o-Ph),41 132.7 (virtual t,40 J CP ) 5.8, o-Ph),41 131.5
(virtual t,40 J CP ) 27.2, i-Ph),41 130.7 (s, CHdCH), 130.2 (br
s, p-Ph),41 128.0 (virtual t,40 J CP ) 5.1, m-Ph),41 31.9 (s, CH2-
CHd), 31.5 (virtual t,40 J CP ) 7.4, PCH2CH2CH2),42 29.22 (s,
CH2), 29.16 (s, CH2), 28.8 (s, double intensity, 2CH2), 27.9 (br
tra ns-(Cl)(C6F5)P t(P P h2(CH2)6CHdCH(CH2)6P P h2)(5b).6c,12
Anal. Calcd for C44H46ClF5P2Pt (pale pink solid, 96%, E/Z 83:
17, mp 193-195 °C): C, 54.92; H, 4.82. Found: C, 55.19; H,
5.00. NMR (δ): 1H (CDCl3) 7.46-7.40 (m, 8 H of 4Ph), 7.30-
7.26 (m, 12 H of 4Ph), 5.38-5.27 (m, 2 H, CHdCH), 2.66-
2.59 (m, 4 H, 2PCH2), 2.25 (m, 4 H, 2CH2CHd), 2.05 (m, 4 H,
2PCH2CH2), 1.48-1.42 (m, 12 H, 6CH2) and (C6D6) 7.67-7.60
(m, 8 H of 4Ph), 7.03-6.99 (m, 12 H of 4Ph), 5.56-5.53/5.52-
5.49 (2 m, CHdCH, Z/E 17:83 (see text)), 2.73-2.69 (m, 4 H,
2PCH2), 2.49 (m, 4 H, 2CH2CHd), 2.19-2.18 (m, 4 H,
2PCH2CH2), 1.57-1.38 (m, 12 H, 6CH2); 13C{1H}39 (CDCl3)
132.7 (virtual t,40 J CP ) 5.5, o-Ph),41 131.8 (virtual t,40 J CP
)
27.6, i-Ph),41 131.1 (s, CHdCH), 130.1 (s, p-Ph),41 128.0 (virtual
t,40 J CP ) 5.5, m-Ph),41 32.0 (s, CH2CHd), 31.9 (virtual t,40 J CP
) 9.2, PCH2CH2CH2),42 28.9 (s, CH2), 28.6 (s, CH2), 27.2 (s,
CH2), 26.8 (virtual t,40 J CP ) 16.6, PCH2);42 31P{1H}44 (CDCl3)
1
s, CH2), 26.5 (br s, CH2), 25.7 (s, CH2); 31P{1H}44 17.6 (s, J PPt
1
) 2675,43 29%), 17.53 (s, < 2%), 17.5 (s, 8%), 17.4 (s, J PPt
)
2670,43 54%), 17.2 (s, 8%). IR (cm-1, powder film): 2964, 2922,
2853, 1502, 1459, 1436, 1262, 1100, 1058, 1019, 953, 799, 737,
691. MS:38 1046 (5d +, < 5%), 1011 ([5d - Cl]+, 100%), 842
([5d - Cl - C6F5]+, 25%).
1
1
17.3 (s, J PPt ) 2679,43 88%), 16.3 (s, J PPt ) 2685,43 12%). IR
(cm-1, powder film): 3057, 2926, 2853, 1502, 1459, 1436, 1104,
1058, 957, 803, 737, 690. MS:38 961 (5b+, 3%), 926 ([5b - Cl]+,
55%), 757 ([5b - Cl - C6F5]+, 20%), 566 ([5b - Cl - C6F5
-
tr a n s-(Cl)(C6F 5)P t(P P h 2(CH2)10P P h 2) (6a ). A Schlenk
flask was charged with 5a (0.131 g, 0.145 mmol), 10% Pd/C
(0.015 g, 0.015 mmol Pd), ClCH2CH2Cl (7.5 mL), and ethanol
(7.5 mL), flushed with H2, and fitted with a balloon of H2. The
mixture was stirred for 100 h. The solvent was removed by
rotary evaporation and oil pump vacuum. Then CH2Cl2 was
added, and the mixture filtered through neutral alumina (5
× 2.5 cm column; rinsed with CH2Cl2). The solvent was
Pt]+, 35%).
tr a n s-(Cl)(C6F5)P t(P P h 2(CH2)8CHdCH(CH2)8P P h 2) (5c).
A two-necked flask was charged with 3c (0.150 g, 0.143 mmol),
4 (ca. half of 0.006 g, 0.0073 mmol, 5 mol %), and CH2Cl2 (60
mL, the resulting solution is 0.0024 M in 3c) and fitted with
(44) The additional signals were tentatively assigned to dimeric or
oligomeric products derived from intermolecular alkene metathesis.
(45) A correct microanalysis could not be obtained for this compound.

5578 Organometallics, Vol. 22, No. 26, 2003
Bauer et al.
removed by rotary evaporation and oil pump vacuum to give
rotary evaporation and oil pump vacuum. Then CH2Cl2 was
added, and the mixture filtered through neutral alumina (3
× 2.5 cm column; rinsed with CH2Cl2). The solvent was
removed by rotary evaporation and oil pump vacuum to give
crude 6c as a white powder (0.190 g, 0.186 mmol, 88%). 31P-
{1H} NMR (δ, CDCl3): 17.6 (s, 81%), 17.4 (s, 9%), 17.3 (s, 10%).
The sample was chromatographed on neutral alumina (10 ×
2.5 cm column) using CH2Cl2/hexanes (1:1 v/v). The solvent
was removed from the product-containing fraction by rotary
evaporation and oil pump vacuum to give 6c as a white powder
(0.127 g, 0.124 mmol, 59%), mp 196-198 °C (capillary), 200
°C (DSC; Ti/Te/Tp/Tc/Tf 178.6/200.2/202.7/204.0/220.6 °C).
crude 6a as a white powder (0.114 g, 0.126 mmol, 87%). 31P-
1
{1H} NMR (δ, CDCl3): 20.5 (s, 9%), 18.7 (s, J PPt ) 2693,43
87%), 16.5 (s, 4%). The sample was chromatographed on
neutral alumina (8 × 2.5 cm column; eluted with 1:1 v/v CH2-
Cl2/hexanes) to give 6a as a white powder (0.092 g, 0.101 mmol,
70%), mp 236-238 °C (capillary), 249 °C (DSC; Ti/Te/Tp/Tc/Tf
226.6/249.5/252.4/253.9/260.2 °C). TGA: onset of mass loss,
321.7 °C (Te). Anal. Calcd for C40H40ClF5P2Pt: C, 52.90; H,
4.44. Found: C, 52.85; H, 4.58. NMR (δ): 1H (CDCl3) 8.06-
8.05 (m, 4 H of 4Ph), 7.52-7.51 (m, 6 H of 4Ph), 7.14-6.91
(m, 10 H of 4Ph), 2.91-2.72 (m, 4 H, 2PCHH′CHH′),46 2.62-
2.51 (m, 2 H, 2PCHH′),46 2.09 (m, 2 H, 2PCHH′CHH′),46 1.66-
1.50 (m, 6 H, 2PCHH′CHH′CHH′CHH′),46 1.36-1.32 (m, 6 H,
2PCHH′CHH′CHH′CHH′CHH′)46 and (toluene-d8) 8.03-8.00
(m, 4 H of 4Ph), 7.15-7.05 (m, 8 H of 4Ph), 6.97-6.80 (m, 4 H
of 4Ph), 6.70-6.61 (m, 4 H of 4Ph), 2.74-2.68 (m, 4 H,
2PCHH′HH′),46 2.25-2.19 (m, 2 H, 2PCHH′),46 2.06-2.03 (m,
2 H, 2PCHH′CHH′),46 1.57-1.43 (m, 12 H, 6CH2); 13C{1H}39
(CDCl3) 134.8 (virtual t,40 J CP ) 6.6, o-Ph),41 132.4 (virtual t,40
J CP ) 26.1, i-Ph),41 131.9 (virtual t,40 J CP ) 27.0, i-Ph′),41 131.0
(s, p-Ph),41 130.4 (virtual t,40 J CP ) 4.9, m-Ph),41 129.2 (s,
p-Ph′),41 128.5 (virtual t,40 J CP ) 5.5, o-Ph′),41 127.4 (virtual
t,40 J CP ) 4.6, m-Ph′),41 29.2 (virtual t,40 J CP ) 8.3, PCH2-
TGA: onset of mass loss, 322.0 °C (Te). Anal. Calcd for C48H56
-
ClF5P2Pt: C, 56.50; H, 5.53. Found: C, 56.29; H, 5.53. NMR
(δ, CDCl3): 1H 7.52-7.49 (m, 8 H of 4Ph), 7.34-7.25 (m, 12 H
of 4Ph), 2.68-2.63 (m, 4 H, 2PCH2), 2.13-2.09 (m, 4 H,
2PCH2CH2), 1.55-1.49 (m, 4 H, 2PCH2CH2CH2), 1.46-1.28
(m, 24 H, 12CH2); 13C{1H}39 132.8 (virtual t,40 J CP ) 5.5,
o-Ph),41 131.2 (virtual t,40 J CP ) 27.4, i-Ph),41 130.1 (s, p-Ph),41
127.9 (virtual t,40 J CP ) 5.1, m-Ph),41 31.2 (virtual t,40 J CP
)
7.8, PCH2CH2CH2),42 28.72 (s, CH2), 28.68 (s, CH2), 28.3 (s,
CH2), 27.87 (s, CH2), 27.84 (s, CH2), 27.3 (s, CH2), 26.1 (virtual
t,40 J CP ) 11.5, PCH2),42 25.8 (s, PCH2CH2);42 31P{1H} 17.6 (s,
1J PPt ) 2679).43 IR (cm-1, powder film): 3061, 2926, 2856, 1502,
1459, 1436, 1262, 1104, 1058, 1027, 957, 803, 737, 691. MS:38
1020 (6c+, 20%), 984 ([6c - Cl]+, 100%), 816 ([6c - Cl - C6F5]+,
45%).
CH2CH2),46 27.1 (s, PCH2CH2CH2CH2), 26.7 (virtual t,40 J CP
)
17.2, PCH2),46 24.9 (s, double intensity, PCH2CH2 + PCH2CH2-
CH2CH2CH2) and (toluene-d8) 135.3 (virtual t,40 J CP ) 6.7,
o-Ph),41 133.1 (s, i-Ph),41 131.9 (virtual t,40 J CP ) 27.0, i-Ph′),41
131.0 (s, p-Ph),41 130.8 (virtual t,40 J CP ) 4.8, m-Ph),41 129.4
(s, p-Ph′),41 29.5 (virtual t,40 J CP ) 8.1, PCH2CH2CH2),46 27.5
(s, PCH2CH2CH2CH2), 27.2 (s, PCH2), 25.4 (s, PCH2CH2CH2-
tr a n s-(Cl)(C6F 5)P t(P P h 2(CH2)20P P h 2) (6d ). A Schlenk
flask was charged with 5d (0.125 g, 0.119 mmol), 10% Pd/C
(0.013 g, 0.011 mmol Pd), ClCH2CH2Cl (6 mL), and ethanol (6
mL), flushed with H2, and fitted with a balloon of H2. The
mixture was stirred for 74 h. The solvent was removed by
rotary evaporation and oil pump vacuum. Then CH2Cl2 was
added, and the mixture filtered through neutral alumina (4
× 2.5 cm column; rinsed with CH2Cl2). The solvent was
removed by rotary evaporation and oil pump vacuum to give
crude 6d as a white powder (0.095 g, 0.0906 mmol, 76%). 31P-
{1H} NMR (δ, CDCl3): 16.8 (s, 8%), 16.6 (s, 86%), 16.5 (s, 6%).
The sample was chromatographed on neutral alumina (7 ×
2.5 cm column) using CH2Cl2/hexanes (1:1 v/v). The solvent
was removed from the product-containing fraction by rotary
evaporation and oil pump vacuum to give 6d as a white powder
(0.062 g, 0.0591 mmol, 50%), mp 122-124 °C (capillary), 139
°C (DSC, Ti/Te/Tp/Tc/Tf 137.7/138.9/143.9/146.0/147.8 °C).
1
CH2CH2); 25.2 (br s, PCH2CH2); 31P{1H} (CDCl3) 18.9 (s, J PPt
) 2694).43 IR (cm-1, powder film): 2934, 2860, 1502, 1463,
1436, 1104, 1058, 957, 803, 737, 691. MS:38 908 (6a +, 20%),
872 ([6a - Cl]+, 100%), 704 ([6a - Cl - C6F5]+, 60%).
tr a n s-(Cl)(C6F 5)P t(P P h 2(CH2)14P P h 2) (6b).6c,12 Anal. Cal-
cd for C44H48ClF5P2Pt (white powder, 94%): C, 54.80; H, 5.02.
Found: C, 54.91; H, 5.23. A chromatographic workup (Sup-
porting Information) gave a sample (72%) that lacked the 31P
NMR impurity below, mp 162-164 °C (capillary), 170 °C (DSC;
Ti/Te/Tp/Tc/Tf 150.0/169.6/172.2/174.0/190.4 °C). TGA: onset of
mass loss, 317.0 °C (Te). NMR (δ): 1H (CDCl3) 7.47-7.42 (m,
8 H of 4Ph), 7.31-7.27 (m, 12 H of 4Ph), 2.67-2.61 (m, 4 H,
2PCH2), 2.13-2.10 (m, 4 H, 2PCH2CH2), 1.50-1.23 (m, 20 H,
10CH2) and (THF-d8) 7.59-7.55 (m, 8 H of 4Ph), 7.36-7.25
(m, 12 H of 4Ph), 2.78-2.72 (m, 4 H, 2PCH2), 2.24-2.22 (m, 4
H, 2PCH2CH2), 1.59-1.33 (m, 20 H, 10CH2); 13C{1H}39 (CDCl3)
TGA: onset of mass loss, 321.7 °C (Te). Anal. Calcd for C50H60
-
ClF5P2Pt: C, 57.28; H, 5.77. Found: C, 57.09; H, 5.72. NMR
(δ, CDCl3): 1H 7.51-7.45 (m, 8 H of 4Ph), 7.35-6.78 (m, 12 H
of 4Ph), 2.68-2.62 (m, 4 H, 2PCH2), 2.07-2.05 (m, 4 H,
2PCH2CH2), 1.55-1.29 (m, 32 H, 16CH2); 13C{1H}39 132.9
(virtual t,40 J CP ) 5.7, o-Ph),41 131.3 (virtual t,40 J CP ) 27.1,
i-Ph),41 130.2 (s, p-Ph),41 127.9 (virtual t,40 J CP ) 5.1, m-Ph),41
31.4 (virtual t,40 J CP ) 7.7, PCH2CH2CH2),42 29.1 (s, CH2), 29.0
(s, CH2), 28.8 (s, CH2), 28.5 (s, CH2), 28.3 (s, CH2), 27.9 (s,
133.8 (virtual t,40 J CP ) 5.4, m-Ph),41 131.4 (virtual t,40 J CP
)
27.5, i-Ph),41 130.1 (s, p-Ph),41 127.9 (virtual t,40 J CP ) 5.3,
m-Ph),41 31.0 (virtual t,40 J CP ) 7.6, PCH2CH2CH2),42 27.7 (s,
CH2), 27.6 (s, CH2), 27.2 (s, CH2), 26.5 (s, CH2), 26.2 (virtual
t,40 J CP ) 16.9, PCH2),42 25.7 (s, PCH2CH2)42 and (THF-d8)
132.8 (virtual t,40 J CP ) 5.7, m-Ph),41 132.7 (virtual t,40 J CP
)
27.1, i-Ph),41 130.8 (s, p-Ph), 128.5 (virtual t,40 J CP ) 5.0,
m-Ph),41 31.8 (virtual t,40 J CP ) 8.2, PCH2CH2CH2),42 28.4 (s,
double intensity, CH2), 28.1 (s, CH2), 27.3 (s, CH2), 26.9 (virtual
t,40 J CP ) 18.0, PCH2),42 26.6 (s, PCH2CH2);42 31P{1H} (CDCl3)
CH2), 27.7 (s, CH2), 26.2 (virtual t,40 J CP ) 17.7, PCH2),42 25.8
1
(s, PCH2CH2);42 31P{1H} 16.6 (s, J PPt ) 2667).43 IR (cm-1
,
powder film): 2926, 2853, 1502, 1463, 1436, 1104, 1058, 957,
803, 737, 691. MS:38 1047 (6d +, 10%), 1012 ([6d - Cl]+, 100%),
843 ([6d - Cl - C6F5]+, 80%).
1
1
17.1 (s, J PPt ) 2670,43 94%), 16.7 (s, J PPt ) 2663,43 6%).44 IR
(cm-1, powder film): 3057, 2926, 2856, 1502, 1459, 1436, 1104,
1061, 957, 803, 741, 691. MS:38 964 ([6b]+, 14%), 928 ([6b -
Cl]+, 100), 760 (50) ([6b - Cl - C6F5]+, 50), 565 ([Ph2P(CH2)14-
PPh2]+, 16%).
Br (CH2)2C(CH3)2(CH2)3CHdCH2 (1e). The dibromide Br-
(CH2)2C(CH3)2(CH2)2Br (6.45 g, 25.0 mmol)21 was added to a
THF solution of Li2CuCl4 (0.10 M, 49.8 mL; see General Data).
The deep orange solution was cooled to 0 °C. Then BrMgCH2-
CHdCH2 (1 M in ether; 50 mL, 50 mmol) was added dropwise
over 30 min with stirring. The mixture became deep green,
then colorless, and finally black. After an additional hour,
aqueous acetic acid (20 mL, 20%) was added. The sample was
extracted with ether (3 × 70 mL). The combined extracts were
washed with saturated aqueous NaHCO3 and dried (MgSO4).
The filtrate was cooled in ice while the solvent was removed
tr a n s-(Cl)(C6F 5)P t(P P h 2(CH2)18P P h 2) (6c). A Schlenk
flask was charged with 5c (0.216 g, 0.212 mmol), 10% Pd/C
(0.023 g, 0.022 mmol Pd), ClCH2CH2Cl (12 mL), and ethanol
(12 mL), flushed with H2, and fitted with a balloon of H2. The
mixture was stirred for 100 h. The solvent was removed by
(46) The aliphatic 1H NMR and 13C NMR signals were assigned from
a
1H,13C COSY spectrum.

Metallamacrocycles via Alkene Metatheses
Organometallics, Vol. 22, No. 26, 2003 5579
by rotary evaporation. The oil was distilled (18 mbar, 40 °C)
to give 1e a colorless liquid (2.20 g, 10.0 mmol, 40%). NMR (δ,
CDCl3): 1H 5.86-5.75 (m, 1 H, CHd), 4.99-4.92 (m, 2 H,
dCH2), 3.38-3.34 (m, 2 H, BrCH2), 2.08-1.98 (m, 2 H, CH2-
CHd), 1.88-1.81 (m, 2 H, BrCH2CH2), 1.33-1.27 (m, 2 H,
CH2), 1.21-1.15 (m, 2 H, CH2), 0.88 (s, 6 H, 2CH3); 13C{1H}
138.8 (s, CHd), 114.5 (s, dCH2), 45.5 (s, BrCH2CH2), 41.2 (s,
C(CH3)3CH2CH2CH2), 34.7 (s, CH2CHd), 29.5 (s, C(CH3)2-
CH2CH2CH2), 27.2 (s, BrCH2), 26.9 (s, double intensity,
C(CH3)2), 23.3 (s, C(CH3)2). IR (cm-1, CDCl3): 3078, 2960, 2935,
2867, 1639, 1388, 1368, 651. MS:38 219 (1e+, 100%).
{1H} NMR of residue (δ, CDCl3): 18.3 (s, 1J PPt ) 2673,43 91%),
17.3 (s, 9%). Then CH2Cl2 was added, and the residue was
filtered through neutral alumina (5 × 2.5 cm column; rinsed
with CH2Cl2). The solvent was removed from the filtrate by
rotary evaporation and oil pump vacuum to give 5e as a pale
pink solid (0.091 g, 0.0893 mmol, 78%; E/Z 88:12). Anal. Calcd
for C48H54ClF5P2Pt: C, 56.61; H, 5.34. Found: C, 56.59; H,
5.47. NMR (δ, CDCl3): 1H 7.52-7.49 (m, 8 H of 4Ph), 7.34-
7.19 (m, 12 H of 4Ph), 5.50-5.47/5.43-5.40 (m, 2 H, CHdCH,
E/Z 88:12 (see text)), 2.69-2.65 (m, 4 H, 2PCH2), 2.02-2.01
(m, 4 H, 2CH2CHd), 1.95-1.91 (m, 4 H, 2PCH2CH2), 1.42-
1.28 (m, 8 H, 4CH2), 0.94 (s, 12 H, 4CH3); 13C{1H}39 132.9
(virtual t,40 J CP ) 6.8, o-Ph),41 131.2 (virtual t,40 J CP ) 27.6,
i-Ph),41 131.0 (s, CHdCH), 130.1 (s, p-Ph),41 127.9 (virtual t,40
J CP ) 5.1, m-Ph),41 40.5 (s, CH2), 36.7 (s, CH2), 33.7 (virtual
t,40 J CP ) 7.1, CH2), 32.7 (s, CH2CHd), 27.0 (s, double intensity,
C(CH3)2), 23.6 (s, CH2), 20.8 (br s, C(CH3)2);47 31P{1H}44 18.3
P P h 2(CH2)2C(CH3)2(CH2)3CHdCH2 (2e). A. A Schlenk
flask was charged with 1e (1.61 g, 7.34 mmol) and THF (10
mL) and cooled to 0 °C. Then KPPh2 (0.5 M in THF, 14.7 mL,
7.34 mmol) was added dropwise with stirring over 0.5 h.35
A
white precipitate formed. After 1 h, the solvent was removed
by oil pump vacuum. Then hexane was added, and mixture
was filtered through neutral alumina (2.5 × 2.5 cm column;
rinsed with hexanes). The solvent was removed by rotary
evaporation. Distillation (9 × 10-3 mbar, 145 °C) gave 2e as a
colorless oil (0.977 g, 3.0 mmol, 41%). Anal. Calcd for
1
(s, J PPt ) 2671,43 91%), 17.3 (s, 9%). IR (cm-1, powder film):
2922, 2845, 1502, 1463, 1436, 1100, 1058, 957, 807, 726, 691.
MS:38 1018 (5e+, <2%), 982 ([5e - Cl]+, 100%), 813 ([5e - Cl
- C6F5]+, 80%).
C
22H29P: C, 81.44; H, 9.01. Found: C, 81.48; H, 9.09. B. An
tr a n s-(Cl)(C6F 5)P t (P P h 2(CH 2)2C(CH 3)2(CH 2)8C(CH 3)2-
otherwise identical reaction of 1e (1.473 g, 6.723 mmol) and
KPPh2 (0.5 M in THF, 13.4 mL, 6.7 mmol) in which the
alumina column was replaced by a simple filtration gave 2e
in 62% yield (1.350 g, 4.161 mmol). NMR (δ, CDCl3): 1H 7.46-
7.38 (m, 4 H of 2Ph), 7.34-7.29 (m, 6 H of 2Ph), 5.82-5.71
(m, 1 H, CHd), 5.02-4.90 (m, 2 H, dCH2), 2.03-1.94 (m, 4 H,
PCH2 + CH2CHd), 1.34-1.15 (m, 6 H, 3CH2), 0.83 (s, 6 H,
(CH2)2P P h 2) (6e). A Schlenk flask was charged with 5e (0.076
g, 0.0746 mmol), 10% Pd/C (0.008 g, 0.008 mmol Pd), ClCH2-
CH2Cl (4.5 mL), and ethanol (4.5 mL), flushed with H2, and
fitted with a balloon of H2. The mixture was stirred for 48 h.
The solvent was removed by rotary evaporation. Then CH2-
Cl2 was added, and the mixture filtered through neutral
alumina (3 × 2.5 cm column; rinsed with CH2Cl2). The solvent
was removed by rotary evaporation and oil pump vacuum to
give the crude 6e as a white powder (0.050 g, 0.0489 mmol,
66%). The sample was chromatographed on neutral alumina
(9 × 2.5 cm column) using CH2Cl2/hexanes (1:1 v/v). The
solvent was removed from the product-containing fraction by
rotary evaporation and oil pump vacuum to give 6e as a white
powder (0.041 g, 0.0402 mmol, 54%), mp 175-177 °C (capil-
lary). Anal. Calcd for C48H56ClF5P2Pt: C, 56.50; H, 5.53.
Found: C, 56.59; H, 5.69. NMR (δ, CDCl3): 1H 7.53-7.50 (m,
8 H of 4Ph), 7.36-7.26 (m, 12 H of 4Ph), 2.70-2.65 (m, 4 H,
2PCH2), 1.86-1.82 (m, 4 H, 2PCH2CH2), 1.34-1.29 (m, 16 H,
2CH3); 13C{1H} 139.2 (s, CHd), 138.9 (d, J CP ) 13.0, i-Ph),36
1
132.7 (d, J CP ) 18.2, o-Ph),36 128.5 (s, p-Ph),36 128.4 (d, J CP
2
3
) 6.5, m-Ph),36 114.3 (s, dCH2), 40.9 (s, CH2CH2CH2CHd),
37.7 (d, J CP ) 16.8, CH2), 34.6 (s, CH2CHd), 33.3 (d, J CP
)
13.1, CH2), 26.9 (s, double intensity, C(CH3)2), 23.3 (s, CH2-
CH2CHd); 22.5 (d, J CP ) 10.5, C(CH3)2);47 31P{1H} -13.6 (s).
3
IR (cm-1, CDCl3): 3074, 2958, 2936, 2867, 1434, 1386, 1365.
MS:38 325 (2e+, 100%).
t r a n s-(C l)(C 6 F 5 )P t (P P h 2 (C H 2 )2 C (C H 3 )2 (C H 2 )3 C H d
CH2)2 (3e). A Schlenk flask was charged with [Pt(µ-Cl)-
(C6F5)(S(CH2CH2-)2)]2 (0.243 g, 0.251 mmol),14 2e (0.325 g,
1.002 mmol), and CH2Cl2 (13 mL). The mixture was stirred
(16 h), and the solvent was removed by oil pump vacuum. The
residue was chromatographed on alumina (11 × 2.5 cm
column) using CH2Cl2/hexanes (1:2 v/v). The solvent was
removed from the product fraction to yield 3e as a colorless
oil (0.330 g, 0.315 mmol, 63%), which solidified after several
days. Anal. Calcd for C50H58ClF5P2Pt: C, 57.39; H, 5.59.
Found: C, 57.25; H, 5.31. NMR (δ, CDCl3): 1H 7.50-7.46 (m,
8 H of 4Ph), 7.33-7.22 (m, 12 H of 4Ph), 5.83-5.73 (m, 2 H,
2CHd), 5.00-4.91 (m, 4 H, 2 dCH2), 2.55-2.52 (m, 4 H,
2PCH2), 2.01-1.98 (m, 4 H, 2CH2CHd), 1.92-1.90 (m, 4 H,
2PCH2CH2), 1.52-1.41 (m, 4 H, 2CH2), 1.33-1.21 (m, 4 H,
2CH2), 0.90 (s, 12 H, 4CH3); 13C{1H}39 138.9 (s, CHd), 132.8
(virtual t,40 J CP ) 6.0 Hz, o-Ph),41 131.1 (virtual t,40 J CP ) 26.7
Hz, i-Ph),41 130.1 (s, p-Ph),41 127.8 (virtual t,40 J CP ) 5.1 Hz,
m-Ph),41 114.3 (s, dCH2), 41.1 (s, CH2), 37.4 (s, CH2), 34.6 (s,
CH2CHd), 33.7 (virtual t,40 J CP ) 7 Hz, CH2), 26.8 (s, double
intensity, C(CH3)2), 23.4 (s, CH2CH2CHd), 21.3 (br s, C(CH3)2);47
8CH2), 0.93 (s, 12 H, 4CH3); 13C{1H}39 133.1 (virtual t,40 J CP
)
5.9, o-Ph),41 130.7 (virtual t,40 J CP ) 27.1, i-Ph),41 130.2 (s,
p-Ph),41 127.9 (virtual t,40 J CP ) 5.0, m-Ph),41 40.2 (s, CH2),
35.1 (s, CH2), 33.6 (virtual t,40 J CP ) 6.6, CH2), 29.4 (s, CH2),
28.0 (s, CH2), 27.8 (s, double intensity, C(CH3)2), 22.7 (s, CH2),
20.6 (virtual t,40 J CP ) 17.6, C(CH3)2);47 31P{1H}44 17.5 (s, 11%),
1
16.4 (s, J PPt ) 2671,43 89%). IR (cm-1, powder film): 2930,
2853, 1502, 1463, 1436, 1104, 1061, 957, 803, 737, 691. MS:38
1019 (6e+, 10%), 984 ([6e - Cl]+, 100%), 816 ([6e - Cl -
C6F5]+, 80%).
Cr ysta llogr a p h y. Toluene solutions of 6a ,c,d were layered
with ethanol and kept at -18 °C (3 days to one month). The
resulting colorless prisms were taken directly to a Nonius
Kappa CCD diffractometer for data collection as outlined in
Table 1. Cell parameters were obtained from 10 frames using
a 10° scan and refined with 16 830, 10 708, and 11 638
reflections, respectively. Lorentz, polarization, and absorption
corrections were applied.48 The space groups were determined
from systematic absences and subsequent least-squares refine-
ment. The structures were solved by direct methods. The
parameters were refined with all data by full-matrix least-
squares on F2 using SHELXL-97.49 Non-hydrogen atoms were
31P{1H} 18.0 (s, J PPt ) 2427 Hz).43 IR (cm-1, powder film):
1
2961, 2934, 2864, 1502, 1463, 1436, 1104, 1058, 957, 911, 807,
737, 691 cm-1. MS:38 1046 (3e+, 3%), 1010 ([3e - Cl]+, 100%),
842 ([3e - Cl - C6F5]+, 20%), 517 ([3e - Cl - C6F5 - PR3]+,
30%).
tr a n s-(Cl)(C6F 5)P t (P P h 2(CH 2)2C(CH 3)2(CH 2)3CH dCH-
(47) The least intense of the aliphatic 13C NMR signals was assigned
to the quaternary carbon.
(48) (a) “Collect” data collection software, Nonius B.V., 1998. (b)
“Scalepack” data processing software: Otwinowski, Z.; Minor, W. In
Methods Enzymol. 1997, 276 (Macromolecular Crystallography, Part
A), 307.
(CH2)3C(CH3)2(CH2)2P P h 2) (5e). A two-necked flask was
charged with 4 (ca. half of 0.009 g, 0.011 mmol, 10 mol %), 3e
(0.120 g, 0.115 mmol), and CH2Cl2 (46 mL, the resulting
solution is 0.0025 M in 3e) and fitted with a condenser. The
solution was refluxed. After 2 h, the remaining 4 was added.
After 3 h, the solvent was removed by rotary evaporation. 31P-
(49) Sheldrick, G. M. SHELX-97, Program for refinement of crystal
structures; University of Go¨ttingen, 1997.

5580 Organometallics, Vol. 22, No. 26, 2003
Bauer et al.
refined with anisotropic thermal parameters. The hydrogen
atoms were fixed in idealized positions using a riding model.
Scattering factors were taken from the literature.50 Two
independent molecules were found in the unit cell of 6a . The
methyl groups of the solvate in 6d ‚(toluene)0.5 were disordered,
but refined to a 50:50 occupancy ratio. Disorder was also
apparent within the aliphatic chain, but could not be resolved
due to the data set quality.
Ack n ow led gm en t. We thank the Deutsche Fors-
chungsgemeinschaft (DFG, GL 300/1-2) and J ohnson
Matthey PMC (platinum and ruthenium loans) for
support, and Dr. Wolfgang Mohr for the synthesis of
phosphine 1d .
Su p p or tin g In for m a tion Ava ila ble: Full experimental
procedures for previously reported compounds (b series)6c,12
and additional crystallographic data for 6a ,c,d . This material
is available free of charge via the Internet at http://pubs.acs.org.
(50) Cromer, D. T.; Waber, J . T. In International Tables for X-ray
Crystallography; Ibers, J . A., Hamilton, W. C., Eds.; Kynoch: Bir-
mingham, England, 1974.
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