A series of ruthenium(II) complexes containing the bulky, functionalized trialkylphosphines tBu2PCH2XC6H5 as ligands

Article abstract of DOI:10.1039/b106243n

The monomeric ruthenium(II) complexes [(η⁶-C₆H₅XCH₂ PtBu₂-κ-P)RuCl₂] 3, 4 were prepared either on a reductive route from RuCl₃·3H₂O and tBu₂PCH₂X

Full text of DOI:10.1039/b106243n

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A series of ruthenium(II) complexes containing the bulky,
functionalized trialkylphosphines tBu2PCH2XC6H5 as ligands
Stefan Jung, Kerstin Ilg, Carsten D. Brandt, Justin Wolf and Helmut Werner*
Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, D-97074 Würzburg,
Germany. E-mail: helmut.werner@mail.uni-wuerzburg.de
Received 13th July 2001, Accepted 30th November 2001
First published as an Advance Article on the web 19th December 2001
The monomeric ruthenium() complexes [(η6-C6H5XCH2PtBu2-κ-P)RuCl2] 3, 4 were prepared either on a reductive
route from RuCl3ؒ3H2O and tBu2PCH2XPh (X = CH2 1, OCH2 2) or by ligand replacement reactions from
[(p-cym)RuCl2]2 and the phosphine via the p-cymene compounds [(p-cym)(C6H5XCH2PtBu2-κ-P)RuCl2] 6, 7 as
intermediates. Abstraction of one chloro ligand from 3 with AgPF6 led to the formation of the dinuclear complex
[{(η6-C6H5CH2CH2PtBu2-κ-P)RuCl}2](PF6)2 8, which reacts with acetone, CH3CN and PMe3 by bridge cleavage
to afford the mononuclear compounds [(η6-C6H5CH2CH2PtBu2-κ-P)RuCl(L)]PF6 9, 10, 12. Both 10 and 11 (the
latter containing 2 as chelating ligand) were also obtained from 3, 4 and AgPF6 in the presence of acetonitrile.
Hydridoruthenium() complexes [(η6-C6H5XCH2PtBu2-κ-P)RuHCl] 13, 14, [RuHCl(H2)(L)2] 15 (L = 1), 16
(L = 2) and [RuHCl(CO)(2)2] 17 could be prepared from RuCl3ؒ3H2O and 1 or 2 in the presence of NEt3 under
reductive conditions. Insertion, substitution and addition reactions of compound 17 led to the formation of
[Ru(CH᎐CH )Cl(CO)(2) ] 18, [RuHF(CO)(2) ] 19, and [RuHCl(CO) (2) ] 20, respectively. The cationic allenylidene
᎐
2
2
2
2
2
complexes [(η6-C H XCH PtBu -κ-P)RuCl(᎐C᎐C᎐CPh )]A 22a,b (X = CH ; A = BF , PF ) and 23 (X = OCH ;
᎐ ᎐ ᎐
6
5
2
2
2
2
4
6
2
᎐
A = PF ) were prepared from 3, 4 or 13, HC᎐CC(OH)Ph and either one equiv. of AgPF or an equivalent
᎐
6
2
6
amount of HBF4 in diethyl ether. Treatment of 15 and 16 with acetylene afforded the five-coordinate
vinylideneruthenium() compounds [RuHCl(᎐C᎐CH )(L) ] 24, 25 which in the presence of HBF are
᎐ ᎐
2
2
4
highly efficient catalysts for the Ring Opening Metathesis Polymerization (ROMP) of cyclooctene.
The molecular structures of 10 and 17 were determined crystallographically.
Carbeneruthenium() complexes of the general composition
Results and discussion
[RuCl (᎐CHR)(PCy )(L)], where L is PCy or an Arduengo
᎐
2
3
3
Half-sandwich-type complexes with tBu2PCH2XPh as ligands
carbene, are at present the most frequently used catalysts for
olefin metathesis.1 Numerous attempts have been made to
modify the coordination sphere of the metal in these five-
coordinate molecules with the hope to find an even better
application profile.2 Taking into consideration that the majority
of carbeneruthenium() compounds described to date have a
16-electron count, it was rather surprising when Dixneuf and
Fürstner recently reported that the cationic 18-electron com-
Recently, we reported that the hydrido(dihydrogen) complex
[RuHCl(H2)(PCy3)2],7 being a convenient starting material
for the preparation of the Grubbs carbenes [RuCl (᎐CHR)-
᎐
2
(PCy3)2],8 can be obtained in a one-pot synthesis from readily
available RuCl3ؒ3H2O.9 Following these studies, we similarly
treated RuCl3ؒ3H2O with the functionalized phosphines 1 and
2 but instead of the anticipated compounds [RuHCl(H2)(L)2]
(L = 1, 2) generated the half-sandwich-type complexes 3 and 4
(Scheme 1) as the dominating species. Since we failed to separ-
ate these compounds from some unidentified by-products, we
plex [(p-cym)RuCl(᎐C᎐C᎐CPh )(PCy )]ϩ catalyzes, although at
᎐ ᎐ ᎐
2
3
higher temperatures, the ring-closure of α,ω dienes.3 Although
the nature of the catalytically active species remains open to
speculation, it was convincingly shown that ruthenium allenyl-
idenes of the type [(η6-arene)RuCl(᎐C᎐C᎐CRЈ )(PR )]ϩXϪ are
᎐ ᎐ ᎐
2
3
excellent catalysts for ring-closing olefin metathesis reactions
(RCM).4
At the time when the first paper by Dixneuf, Fürstner et al.
appeared,3 we had begun to study the coordinating capabilities
of bulky trialkylphosphines having a phenyl group in one of the
alkyl side-chains. After we prepared a variety of cationic half-
sandwich-type rhodium complexes with R2P(CH2)nPh (n = 2, 3)
and R2P(CH2)2OPh (R = iPr, tBu) as ligands and, in the context
of these studies, also found that these new phosphines can bind
to rhodium in different modes,5 we became interested to find
out how the same phosphines behave toward other transition-
metals. In this article we report the synthesis of a series of
neutral and cationic ruthenium() complexes in which the
bulky phosphines tBu2P(CH2)2Ph 1 and tBu2P(CH2)2OPh 2
are coordinated either via the six-membered ring and the phos-
phorus atom or only via the P-donor to the metal centre. A
preliminary account of these results has already been given.6
Scheme 1
318
J. Chem. Soc., Dalton Trans., 2002, 318–327
This journal is © The Royal Society of Chemistry 2002
DOI: 10.1039/b106243n

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Table 1 Selected bond lengths (Å) and angles (Њ) for compound 10
looked for a second synthetic route and found that the method
developed by Smith and Wright10 for [{η6-C6H5(CH2)3PPh2-
κ-P}RuCl2] can also be applied for the preparation of pure
samples of 3 and 4. The first step of this procedure consists of
the conversion of the dimeric starting material 5 to the mono-
meric (p-cymene)ruthenium complexes 6 and 7 which upon
heating in chlorobenzene at 130 ЊC for 18 h afford the target
molecules 3 and 4 in nearly quantitative yields. Like other com-
pounds of the general composition [(p-cym)RuCl2(PR3)],11 the
intermediates 6 and 7 are air-stable microcystalline solids
which are readily soluble in polar solvents such as acetone or
dichloromethane.
Ru–P1
Ru–Cl
Ru–N
Ru–C1
Ru–C2
2.3976(13)
2.4201(13)
2.050(4)
2.163(5)
2.196(5)
Ru–C3
Ru–C4
Ru–C5
Ru–C6
N–C10
2.209(5)
2.270(5)
2.265(5)
2.183(5)
1.146(6)
P1–Ru–Cl
Cl–Ru–N
P1–Ru–N
Ru–P1–C8
93.98(5)
85.26(12)
94.38(12)
102.28(17)
Ru–P1–C20
Ru–P1–C21
Ru–N–C10
N–C10–C11
118.47(16)
114.72(17)
176.3(4)
176.5(5)
The clean intramolecular substitution reaction of 3 and 4 to
give 6 and 7 deserves a comment insofar as the previously
described complexes [{η6-1,2-C6H4(CH2OH)CH2CH2PPh2-
κ-P}RuCl2]12 and [{η6-C6H5(CH2)3PPh2-κ-P}RuCl2]10 were
obtained from the corresponding p-cymene precursors in only
small to moderate yields. Based on our experience with arene-
ruthenium() compounds with sterically demanding non-
chelating phosphine ligands,13 we assume that the bulkiness of
the tert-butyl substituents at phosphorus facilitates the dis-
placement of the p-cymene unit and also hinders side-reactions
such as the intermolecular attack of the phenyl ring of a second
molecule of 6 or 7 to the ruthenium centre. Regarding the
spectroscopic data of 3 and 4, a typical feature is that the reson-
ances of the carbon atoms of the C6H5 fragment are signifi-
cantly shifted to higher fields compared with the intermediates
6 and 7.
The half-sandwich-type compound 3 reacts with one equiv.
of AgPF6 in acetone to give an orange–yellow solution from
which, upon addition of pentane, orange–yellow crystals pre-
cipitated. In contrast to what we expected, the isolated product
is not the monomeric solvento complex [(η6-C6H5CH2CH2P-
tBu2-κ-P)RuCl(acetone)]PF6 but the PF6-salt of the dicationic
species 8 (Scheme 2). The composition of 8 was confirmed both
Scheme 3
atoms indicating that, in agreement with the presence of a
chiral centre in the cations, all the CH units of the phenyl
groups are stereochemically different. The 31P NMR spectrum
of 12 displays two doublet resonances at δ 89.2 and Ϫ7.5 with a
31P–31P coupling constant of 48.0 Hz.
The molecular structure of compound 10 was confirmed by
a single-crystal X-ray diffraction study. The ORTEP15 plot
(Fig. 1) illustrates the three-legged piano-stool configuration of
Scheme 2
by elemental analysis and conductivity measurements. In
acetone-d6 as solvent, the chloro bridges of 8 are split and the
mononuclear complex 9 is formed. The reaction is completely
reversible since after removal of the solvent the dinuclear
precursor 8 is regenerated quantitatively.
Fig. 1 Molecular structure of 10.
the cation as well as the chelating bonding mode of the func-
tionalized phosphine. The bond lengths between the metal and
the ring carbon atoms differ between 2.163(5) and 2.270(5) Å,
the longest distances (Ru–C4 and Ru–C5) being found trans to
the phosphorus atom. In contrast to the cationic rhodium com-
plex [(η6-C6H5CH2CH2PiPr2-κ-P)Rh(C8H14)]ϩ,5 the phenyl ring
is nearly planar and does not show a boat conformation. The
bond angles P1–Ru–Cl, P1–Ru–N and N–Ru–Cl (see Table 1)
are near to 90Њ which is in agreement with the pseudo-
octahedral geometry of the molecule.
In contrast to 9, the corresponding acetonitrileruthenium()
derivatives 10 and 11 are significantly more stable and can be
prepared either from 3 or 4 and AgPF6 in CH2Cl2–CH3CN or,
for tBu2PCH2CH2Ph as the ligand, from 8 and acetonitrile
(Scheme 3). Treatment of 10 with an equimolar amount of
PMe3 leads to a ligand exchange and the formation of 12. This
cationic trimethylphosphineruthenium() complex is also
accessible from 8 and PMe3. Compounds 10 and 11 as well as
12 are yellow microcrystalline solids which are readily soluble in
polar organic solvents and, in nitromethane, possess the con-
Hydridoruthenium(II) complexes with tBu2PCH2XPh as ligands
1
ductivity of 1 : 1 electrolytes.14 The H NMR spectra of 10–12
display five resonances for the C6H5 ring protons and the 13C
Ruthenium() complexes with one hydride and the functional-
ized phosphine 1 or 2 either as chelating or merely P-bonded
NMR spectra six signals for the corresponding ring carbon
J. Chem. Soc., Dalton Trans., 2002, 318–327
319

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Table 2 Selected bond lengths (Å) and angles (Њ) for compound 17
ligand are also accessible from RuCl3ؒ3H2O as the starting
material. The procedure to prepare the chloro(hydrido) com-
pounds 13 and 14 (Scheme 4) is different to that for the dichloro
Ru–C1
Ru–Pl
Ru–P2
1.825(7)
2.3959(14)
2.4021(14)
Ru–Cl
C1–O3
2.4187(18)
1.140(9)
P1–Ru–P2
P1–Ru–C1
P1–Ru–Cl
P2–Ru–C1
176.66(5)
88.55(17)
91.16(6)
P2–Ru–Cl
Ru–C1–O3
C1–Ru–Cl
91.61(6)
178.1(6)
157.26(19)
89.62(17)
Scheme 4
derivatives 3 and 4 only insofar as the in situ generated inter-
16
mediate [(η3:η3-C10H16)RuCl2]2 is treated with the phosphine
in methanol or boiling THF under a hydrogen atmosphere
in the presence of one equiv. of NEt3. In both cases, the yield of
the chelate complexes is nearly quantitative. Compound 14,
which like 13 is a yellow air-sensitive solid, is somewhat less
stable than the non-oxygen containing counterpart 13 and
decomposes quite rapidly in benzene. The 1H NMR spectra of
13 and 14 display a high-field resonance at around δ Ϫ7.5 which
is split into a doublet due to 31P–1H coupling.
Fig. 2 Molecular structure of 17.
Ru–C1 of 17 is ca. 0.07 Å longer than that of the bis(triiso-
propylphosphine) compound. We assume that this increase is
due to the non-linearity of the Cl–Ru–C1 unit.
Compound 17 does not only react with acetylene and CsF by,
respectively, insertion and substitution but owing to the pres-
ence of a coordinatively unsaturated metal centre also with CO
to give the 18-electron complex 20 (Scheme 5). The products of
If the above-mentioned intermediate [(η3:η3-C10H16)RuCl2]2
reacts with 1 or 2 and NEt3 in THF under H2 at room temper-
ature for 1 h instead of 80 ЊC for 24 h, the five-coordinate
hydrido(dihydrogen)ruthenium() complexes 15 and 16 are
produced in moderate to good yields. By treating the inter-
mediate with 2 in methanol a mixture of 16 and 17 is generated.
If this mixture is stirred at 80 ЊC for 6 h, in the absence of H2, the
hydrido(carbonyl) compound 17 is formed exclusively. In con-
trast to 17, the hydrido(dihydrogen) complexes 15 and 16 are
low-melting solids which are considerably more air-sensitive
than the corresponding chelate compounds 13 and 14. The
most characteristic spectroscopic feature of 15 and 16 is the
broadened signal for the protons of the RuH(H2) fragment at
Scheme 5
1
δ Ϫ16.53 (15) and Ϫ16.63 (16) in the H NMR spectra, the
the reactions of 17 with C2H2 and CsF are the five-coordinate
vinyl- and fluoro-(hydrido)ruthenium() compounds 18 and 19
which presumably possess a similar structure to that of the
starting material 17. We note that the bis(triisopropylphos-
phine) complexes [MHCl(CO)(PiPr3)2] (M = Ru, Os) equally
react with acetylene and phenylacetylene by insertion into the
M–H bond to yield the corresponding vinyl-ruthenium() and
-osmium() derivatives.19
The coordinatively saturated dicarbonyl compound 20 is not
only accessible from 17 and CO but also directly in a one-pot
synthesis from RuCl3ؒ3H2O probably via [(η3:η3-C10H16)RuCl2]2
and 15 as intermediates (Scheme 6). In contrast to 17, the
18-electron complex 20 is completely inert towards terminal
alkynes. The reaction of 20 with CsF in acetone leads to the
formation of the substitution product 21, being in analogy to
20 thermally much more stable than the monocarbonyl com-
pound 19. Since the 13C NMR spectra of both 20 and 21 display
two resonances at δ 201.1, 200.1 (20) and δ 203.1, 200.1 (21), we
conclude that the two CO ligands are not trans but cis disposed.
chemical shift being similar to that of the analogue [RuHCl-
(H2)(PCy3)2] (δ Ϫ16.8).7 The presence of one resonance in the
31P NMR spectra of 15 and 16 (as well as of 17) indicates that
the two phosphorus atoms are trans disposed.
The result of the X-ray crystal structure analysis of 17 is
shown in Fig. 2. Although the position of the hydrido ligand
could not be exactly located, the coordination geometry around
the ruthenium centre is best described as a distorted square-
pyramid with the hydride in the apical position. While the
P1–Ru–P2 axis is almost linear (see Table 2), the bond angle
Cl–Ru–C1 (157.26(19)Њ) deviates significantly from the ideal
value of 180Њ which is possibly due to steric hindrance between
the sterically demanding substituents at the phosphorus atoms
and the carbonyl and the chloro ligands. For the related hydrido-
ruthenium() complex [RuHCl(CO)(PiPr3)2] with the less bulky
triisopropylphosphine,17 the bond angle P–Ru–P is 177.3(2)Њ.18
While the distances Ru–P1, Ru–P2 and Ru–Cl of 17 and
[RuHCl(CO)(PiPr3)2] are nearly identical, the bond length
320
J. Chem. Soc., Dalton Trans., 2002, 318–327

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already at 58 ЊC. The 13C NMR spectra of both 24 and 25
display in the low-field region the typical resonances for the α-
and β-carbon atoms of the vinylidene ligand at δ 326.5 and 87.9
(for 24) and δ 328.1 and 90.0 (for 25) which are split into triplets
1
due to 13C–31P coupling. In the H NMR spectra the signal
for the RuH proton also appears as a triplet at δ Ϫ15.80 (for
24) and δ Ϫ14.85 (for 25). With regard to the structure of 24
and 25, we note that recently Olivan, Eisenstein and Caulton
reported the preparation of the compound [RuHCl(᎐C᎐CHR)-
᎐ ᎐
(PtBu2Me)2] (R = Ph, SiMe3) which according to ab initio DFT
calculations possess instead of a square-pyramidal a distorted
trigonal-bipyramidal geometry with the two phosphines in the
apical positions.23
Scheme 6 (L = 2).
The assumption that one carbonyl is trans to hydride is further
supported by the chemical shift of the signal for the RuH
proton at δ Ϫ5.51 (20) and Ϫ4.31 (21), which appears upfield by
ca. 20 ppm compared to the five-coordinate counterparts where
the position trans to hydride is unoccupied. The IR spectra
of 20 and 21 also show two bands in the metal-carbonyl
region indicating that the two CO groups are stereochemically
inequivalent.
The reactions of both 24 and 25 with an ethereal solution of
HBF4 at room temperature leads to a mixture of products in
which, after removal of the solvent, only the phosphonium
salt [HPtBu2CH2XPh]BF4 could be unambiguously identified.5
However, if a solution of HBF4 in ether is added to a solution
of 24 in CD2Cl2 at Ϫ78 ЊC, the 1H NMR spectrum indicates the
formation of the carbyneruthenium cation 26 (see Scheme 8).
Owing to the chemical shift of the hydride signal at δ Ϫ7.63,
which is quite similar to that of the pseudo-octahedral com-
plexes 13 and 14, we assume that the cation 26 has an 18-
electron configuration with a solvent molecule coordinated
trans to the carbyne moiety. An analogous structure has been
Allenylidene and vinylidene complexes with tBu2PCH2XPh as
ligands
Similarly to 20, the chloro(hydrido) compound 13 having also
an 18-electron configuration is inert towards acetylene and
HC᎐CC(OH)Ph . If, however, the reaction of 13 with the sub-
stituted propargylic alcohol is carried out in the presence of an
equimolar amount of HBF4 in diethyl ether, the cationic
allenylidene complex 22a is obtained in practically quantitative
yield. Treatment of the dichloro derivative 3 with HC᎐CC-
(OH)Ph2 and one equiv. of AgPF6 in acetone affords the cor-
responding PF6 salt 22b (Scheme 7). The preparation of the
related complex 23 with tBu2PCH2CH2OPh as ligand proceeds
on the same route. 22a,b as well as 23 are violet, rather air-
sensitive solids which in nitromethane show the conductivity of
1 : 1 electrolytes. Typical spectroscopic features of the allenyl-
ϩ
᎐
proposed for the related cation [RuHCl(᎐CCH )(OEt )(PCy ) ]
᎐
3
2
3 2
᎐
᎐
2
which is a good catalyst both for the Ring Opening Metathesis
Polymerization (ROMP) of cyclooctene as well as for the cross-
olefin metathesis of cyclopentene with methylacrylate.22
᎐
The in situ generated cations [RuHCl(᎐CCH )(OEt )(tBu -
᎐
3
2
2
᎐
᎐
PCH2XPh)2]ϩ (X = CH2, OCH2) also catalyze the ROMP of
cyclooctene. As shown in Fig. 3, the rate of formation of the
ideneruthenium cations are the strong C᎐C᎐C stretching mode
᎐ ᎐
at ca. 1970 cmϪ1 in the IR spectra and, in the 13C NMR spec-
trum of 22b, the three low-field resonances at around δ 285.2,
178.5 and 172.0, the latter being assigned to the α-, β- and
γ-carbon atoms of the C3Ph2 moiety.20 It should be mentioned
that recently the groups of Fürstner and Dixneuf prepared
not only a series of areneruthenium() complexes [(η6-arene)-
RuCl(PR )(᎐C᎐C᎐CRЈ )]PF but also the chelate compound
᎐ ᎐ ᎐
3
2
6
[{η6-C H (CH ) PCy -κ-P}RuCl(᎐C᎐C᎐CPh )](O SCF ) which
᎐ ᎐ ᎐
6
5
2
3
2
2
3
3
is a close relative of 23.3,4,21
Fig. 3 ROMP of cyclooctene using 24, 25 (both in the presence of 4
µmol HBF4) and [RuCl2(᎐᎐CHPh)(PCy3)2] (A) as catalysts. Conditions:
21 ЊC, 81.4 µl (625 µmol) C8H14, 0.5 µmol ruthenium compound,
CD2Cl2–OEt2 as solvent. Yield of polymer determined by 1H NMR
spectroscopy.
Following the observation that the hydrido(dihydrogen)-
ruthenium complexes [RuHCl(H2)(PiPr3)2] and [RuHCl(H2)-
(PCy3)2] react with acetylene to give the five-coordinate hydrido-
(vinylidene) derivatives [RuHCl(᎐C᎐CH )(PR ) ] (R = iPr, Cy),22
᎐ ᎐
2
3 2
we were prompted to study also the reactivity of compounds 15
and 16 towards C2H2. Passing a slow stream of acetylene
through a solution of the starting material in dichloromethane
at Ϫ78 ЊC affords indeed the anticipated vinylidene complexes
24 and 25 in ca. 90–95% yield (Scheme 8). The orange–brown
or light brown solids are quite air-sensitive and decompose
polymer is significantly higher than by using the well-known
Grubbs carbene [RuCl (᎐CHPh)(PCy ) ] as the catalyst. Under
᎐
2
3 2
identical conditions (CD2Cl2, 21 ЊC, ratio cyclooctene to
ruthenium complex = 1250 : 1), the polymerization of C8H14
with the mixture of 25/HBF4 as catalyst is finished after ca. 8
Scheme 7
J. Chem. Soc., Dalton Trans., 2002, 318–327
321

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occurred. After cooling to room temperature the solvent was
evaporated in vacuo, the remaining light brown solid was
repeatedly washed with pentane, and dried in vacuo. The solid
(320 mg) was dissolved in THF (20 cm3), the solution was
treated with 1 (638 mg, 2.55 mmol), and the reaction mixture
was stirred under a H2 atmosphere for 3 h at 70 ЊC. During that
time a gradual change of colour from brown to orange–brown
took place and an orange solid precipitated. The solvent was
removed in vacuo, the residue was washed four-times with 8 cm3
portions of ether, and dried in vacuo; yield 342 mg (95%).
Method B. A solution of compound 6 (355 mg, 0.64 mmol) in
chlorobenzene (25 cm3) was heated for 18 h at 130 ЊC. After
cooling to room temperature, the solution was concentrated to
ca. 2 cm3 in vacuo and stored for 2 h. An orange solid precipi-
tated, which was separated from the mother liquor, washed
twice with 10 cm3 portions of ether and dried in vacuo; yield 267
mg (98%); mp 188 ЊC (decomp.) (Found: C, 45.39; H, 6.59.
C16H27Cl2PRu requires: C, 45.50; H, 6.44%). NMR (CD2Cl2):
δH (400 MHz) 6.08 (1 H, m, para-H of C6H5), 5.77, 5.15 (2 H
each, both m, C6H5), 2.96 (2 H, m, CH2Ph), 2.66 (2 H, m,
PCH2), 1.40 [18 H, d, J(P,H) 13.2, PCCH3]; δC (100.6 MHz)
110.7 [d, J(P,C) 4.8, ipso-C of C6H5], 96.5 [d, J(P,C) 2.9, C6H5],
90.3 [d, J(P,C) 13.5, C6H5], 77.5 (s, C6H5), 37.9 [d, J(P,C) 11.4,
PCCH3], 35.2 [d, J(P,C) 22.9, PCH2], 32.0 [d, J(P,C) 3.8,
CH2Ph], 29.7 (s, PCCH3); δP (162.0 MHz) 85.8 (s). EI MS
(70 eV): m/z 422 (Mϩ, 16.7), 387 (Mϩ Ϫ Cl, 16.3), 352 (Mϩ Ϫ 2
Cl, 4.3%).
Scheme 8
min whereas with the carbene compound in the same period of
time only ca. 15% of the olefin is polymerized. A reasonable
explanation for the remarkable difference in rate is that the dis-
sociation of one phosphine ligand, being the rate-determining
step in the catalysis with [RuCl (᎐CHPh)(PCy ) ],24 pro-
᎐
2
3 2
ceeds much faster in the case of the carbyneruthenium cations
which in general are considerably more labile than the neutral
ruthenium carbenes.
In summary, the work presented in this paper has shown that
the functionalized phosphines 1 and 2 having two bulky tert-
butyl groups at the phosphorus atom coordinate either as
chelating 8-electron or P-bonded 2-electron donor ligands to
ruthenium() as the metal centre. By using the readily available
RuCl3ؒ3H2O as the starting material it is possible not only to
prepare the chelate complexes [(η6-C6H5XCH2PtBu2-κ-P)-
RuCl2] 3, 4 and [(η6-C6H5XCH2PtBu2-κ-P)RuHCl] 13, 14 but
also a series of five-coordinate hydridoruthenium() com-
pounds [RuHCl(LЈ)(L)2] of which that with LЈ = CO and L = 2
smoothly undergoes insertion, substitution and addition reac-
tions with appropriate nucleophilic substrates. Cationic allenyl-
idene complexes with 1 or 2 as chelating ligands are accessible
both from 3, 4 and from 13, while neutral vinylideneruth-
[(ꢀ6-C6H5OCH2CH2PtBu2-ꢁ-P)RuCl2] 4. Method A. This
compound was prepared as described for 3, from RuCl3ؒ3H2O
(126 mg, 0.48 mmol) and isoprene (1.5 cm3, 15.0 mmol) in iso-
propanol (6 cm3). The light brown solid (180 mg) was dissolved
in THF (20 cm3), treated with 2 (321 mg, 1.21 mmol) and the
reaction mixture was stirred under a H2 atmosphere for 16 h at
70 ЊC. After cooling to room temperature, the solvent was
removed in vacuo, the orange residue was repeatedly washed
with ether, and dried in vacuo; yield 107 mg (51%).
Method B. The procedure was analogous to that described
for 3, using 7 (246 mg, 0.43 mmol) as starting material. Orange
solid: yield 165 mg (88%); mp 168 ЊC (decomp.) (Found: C,
43.33; H, 6.41. C16H27Cl2OPRu requires: C, 43.84; H, 6.21%).
NMR (CD2Cl2): δH (400 MHz) 6.01 (1 H, m, para-H of C6H5),
5.88, 5.14 (2 H each, both m, C6H5), 4.54 (2 H, m, CH2OPh),
2.14 (2 H, m, PCH2), 1.39 [18 H, d, J(P,H) 13.2, PCCH3]; δC
(100.6 MHz) 124.6 (s, ipso-C of C6H5), 98.7 [d, J(P,C) 2.0,
C6H5], 88.8 [d, J(P,C) 13.2, C6H5], 70.0 (s, C6H5), 69.9 (s,
CH2OPh), 38.1 [d, J(P,C) 14.2, PCCH3], 30.3 [d, J(P,C) 2.0,
PCCH3], 16.2 [d, J(P,C) 17.3, PCH2]; δP (162.0 MHz) 37.0 (s).
EI MS (70 eV): m/z 438 (Mϩ, 1.4), 403 (Mϩ Ϫ Cl, 4.1), 368 (Mϩ
Ϫ 2 Cl, 2.0%).
enium() compounds [RuHCl(᎐C᎐CH )(L) ] 24, 25 can be
᎐ ᎐
2
2
prepared from the hydrido(dihydrogen) derivatives [RuH-
Cl(H2)(L)2] 15, 16 by treatment with acetylene. In the presence
of HBF4, the vinylidene complexes are excellent catalysts
for ROMP of cyclooctene being even more efficient than the
Grubbs carbene.
Experimental
All experiments were carried out under an atmosphere of argon
by Schlenk techniques. The starting materials tBu2P(CH2)2Ph
1,5 tBu2P(CH2)2OPh 2,5 and [(η6-MeC6H4CHMe2)RuCl2]2 5,25
were prepared as described in the literature. The propargylic
alcohol HC᎐CC(OH)Ph was a commercial product from
Aldrich. NMR spectra were recorded at room temperature on
Bruker AC 200, Bruker DRX 300 and Bruker AMX 400
instruments, IR spectra on a Perkin-Elmer 1420 or an IFS 25
FT-IR infrared spectrometer, and mass spectra (EI MS, FAB
MS) on a Finnigan 90 MAT spectrometer. Melting points were
measured by DTA, and molar conductivities, Λ, were deter-
mined in CH3NO2. Abbreviations used: s, singlet; d, doublet;
t, triplet; vt, virtual triplet; m, multiplet; br, broadened signal;
[(ꢀ6-MeC6H4CHMe2)(C6H5CH2CH2PtBu2-ꢁ-P)RuCl2] 6. A
solution of 5 (500 mg, 0.82 mmol) in CH2Cl2 (18 cm3) was
treated with 1 (511 mg, 2.04 mmol) and stirred for 6 h at 30 ЊC.
The solution was filtered and the solvent was evaporated in
vacuo. The remaining red–brown solid was washed three times
with 15 cm3 portions of pentane, and dried in vacuo; yield
819 mg (90%); mp 125 ЊC (decomp.) (Found: C, 55.63; H, 7.00.
C26H41Cl2PRu requires: C, 56.11; H, 7.42%). NMR (CD2Cl2):
δH (400 MHz) 7.22–7.10 (5 H, m, C6H5), 5.68 (4 H, m, C6H4),
3.07 (2 H, m, CH2Ph), 2.85 [1 H, sept, J(H,H) 7.0, CHCH3],
2.13 (3 H, s, CH3C6H4), 2.12 (2 H, m, PCH2), 1.46 [18 H, d,
J(P,H) 12.0, PCCH3], 1.32 [6 H, d, J(H,H) 7.0, CHCH3]; δC
(100.6 MHz) 144.6 [d, J(P,C) 12.2, ipso-C of C6H5], 128.3,
128.2, 125.6 (all s, C6H5), 106.7, 95.6 (both s, tert-C of C6H4),
88.3 [d, J(P,C) 4.1, C6H4], 84.2 [d, J(P,C) 5.1, C6H4], 81.2, 80.5
(both s, C6H4), 39.1 [d, J(P,C) 12.2, PCCH3], 32.2 (s, CH2Ph),
31.2 [d, J(P,C) 3.1, PCCH3], 30.7 (s, CHMe2), 25.4 [d, J(P,C)
15.3, PCH2], 22.5 (s, CH3C6H4), 17.8 (s, CHCH3); δP (162.0
MHz) 46.1 (s).
᎐
᎐
2
3
5
coupling constants J and N in Hz; N = J(PH) ϩ J(PH) or
2J(PC) ϩ 4J(PC).
Preparations
[(ꢀ6-C6H5CH2CH2PtBu2-ꢁ-P)RuCl2] 3. Method A. A solution
of RuCl3ؒ3H2O (222 mg, 0.85 mmol) in isopropanol (12 cm3)
was treated with isoprene (2 cm3, 0.02 mol) and stirred for 6 h at
80 ЊC. A change of colour from dark green to red–brown
322
J. Chem. Soc., Dalton Trans., 2002, 318–327

View Article Online
[(ꢀ6-MeC6H4CHMe2)(C6H5OCH2CH2PtBu2-ꢁ-P)RuCl2] 7.
This compound was prepared as described for 6, from 5 (306
mg, 0.50 mmol) and 2 (373 mg, 1.40 mmol) in CH2Cl2 (18 cm3);
reaction time 3 h. Light brown solid: yield 500 mg (87%); mp
110 ЊC (decomp.) (Found: C, 54.64; H, 6.72. C26H41Cl2OPRu
requires: C, 54.54; H, 7.22%). NMR (CD2Cl2): δH (400 MHz)
7.22–6.83 (5 H, m, C6H5), 5.74–5.64 (4 H, m, C6H4), 4.36 (2 H,
m, CH2OPh), 2.80 [1 H, sept, J(H,H) 7.0, CHCH3], 2.21 (2 H,
m, PCH2), 2.11 (3 H, s, CH3C6H4), 1.44 [18 H, d, J(P,H) 12.3,
PCCH3], 1.32 [6 H, d, J(H,H) 7.0, CHCH3]; δC (100.6 MHz)
159.0 (s, ipso-C of C6H5), 129.3, 120.0, 114.6 (all s, C6H5), 106.5,
96.3 (both s, tert-C of C6H4), 88.3, 84.7 [both d, J(P,C) 4.1,
C6H4], 81.2, 80.5 (both s, C6H4), 66.5 [d, J(P,C) 3.1, CH2OPh],
39.1 [d, J(P,C) 13.2, PCCH3], 30.9 [d, J(P,C) 3.1, PCCH3], 30.6
(s, CHMe2), 22.8 [d, J(P,C) 19.3, PCH2], 22.5 (s, CH3C6H4),
17.8 (s, CHCH3); δP (162.0 MHz) 46.9 (s).
NP2Ru requires: C, 37.74; H, 5.28; N, 2.44%). Λ 96.3 cm2 ΩϪ1
molϪ1. IR (KBr): ν(CN) 2328, ν(PF6Ϫ) 843 cmϪ1. NMR
(CD2Cl2): δH (300 MHz) 6.38, 6.29, 5.95, 5.57, 5.34 (1 H each,
all m, C6H5), 3.17–2.82, 2.70–2.58 (2 H each, all m, PCH2-
CH2Ph), 2.53 (3 H, s, CH3CN), 1.41 [9 H, d, J(P,H) 14.2,
PCCH3], 1.34 [9 H, d, J(P,H) 13.6, PCCH3]; δC (75.5 MHz)
128.6 (s, CN), 116.0 [d, J(P,C) 5.1, ipso-C of C6H5], 98.1 [d,
J(P,C) 1.5, C6H5], 97.1 [d, J(P,C) 3.6, C6H5], 92.3 [d, J(P,C) 10.5,
C6H5], 80.3, 78.4 (both s, C6H5), 38.8 [d, J(P,C) 14.5, PCCH3],
36.4 [d, J(P,C) 12.4, PCCH3], 35.8 [d, J(P,C) 24.3, PCH2], 31.9
[d, J(P,C) 2.2, CH2Ph], 29.6 [d, J(P,C) 1.5, PCCH3], 29.4 [d,
J(P,C) 3.3, PCCH3], 4.5 (s, CH3CN); δP (81.0 MHz) 97.0 (s),
Ϫ143.9 [sept, J(F,P) 711.2, PF6Ϫ]. FAB MS (70 eV): m/z 573
(Mϩ, 0.04), 428 (Mϩ Ϫ PF6, 0.1), 387 (Mϩ Ϫ PF6 Ϫ MeCN,
2.3), 352 (Mϩ Ϫ Cl Ϫ PF6 Ϫ MeCN, 0.3%).
[(ꢀ6-C6H5OCH2CH2PtBu2-ꢁ-P)RuCl(NCMe)]PF6 11. This
compound was prepared as described for 10, Method A, from
4 (75 mg, 0.17 mmol) in CH2Cl2–CH3CN (2 : 1, 15 cm3) and
AgPF6 (44 mg, 0.17 mmol) in CH2Cl2 (3 cm3); reaction time
50 min. Yellow solid: yield 82 mg (82%); mp 156 ЊC (decomp.)
(Found: C, 36.89; H, 5.01; N, 2.46. C18H30ClF6NOP2Ru
requires: C, 36.71; H, 5.13; N, 2.38%). Λ 91.6 cm2 ΩϪ1 molϪ1. IR
(KBr): ν(CN) 2325, ν(PF6Ϫ) 837 cmϪ1. NMR (CD2Cl2): δH
(400 MHz) 6.30, 6.14, 6.02, 5.33, 5.16 (1 H each, all m, C6H5),
4.75–4.52 (2 H, m, CH2OPh), 2.45 (3 H, s, CH3CN), 2.27–2.04
(2 H, m, PCH2), 1.34 [9 H, d, J(P,H) 14.1, PCCH3], 1.26 [9 H, d,
J(P,H) 13.5, PCCH3]; δC (100.6 MHz) 129.4 (s, CN), 128.0 (s,
ipso-C of C6H5), 101.5, 98.9 (both s, C6H5), 89.1 [d, J(P,C) 11.2,
C6H5], 71.3, 70.7 (both s, C6H5), 69.4 (s, CH2OPh), 38.8 [d,
J(P,C) 16.3, PCCH3], 36.1 [d, J(P,C) 14.2, PCCH3], 30.7, 29.6
(both s, PCCH3), 15.8 [d, J(P,C) 19.3, PCH2], 4.6 (s, CH3CN);
δP (162.0 MHz) 48.6 (s), Ϫ144.3 [sept, J(F,P) 713.2, PF6Ϫ].
[{(ꢀ6-C6H5CH2CH2PtBu2-ꢁ-P)RuCl}2](PF6)2 8. A suspension
of 3 (59 mg, 0.14 mmol) in acetone (8 cm3) was treated dropwise
with a solution of AgPF6 (35 mg, 0.14 mmol) in acetone (5
cm3). After the reaction mixture was stirred for 75 min at room
temperature, an orange–yellow solution resulted from which a
white solid precipitated. The solution was filtered and the
filtrate was concentrated in vacuo to ca. 2 cm3. Addition of
pentane (10 cm3) led to the formation of orange–yellow crys-
tals, which were separated from the mother liquor, washed twice
with 5 cm3 portions of pentane and dried in vacuo; yield 46 mg
(61%); mp 178 ЊC (decomp.) (Found: C, 36.68; H, 4.79.
C32H54Cl2F12P4Ru2 requires: C, 36.13; H, 5.11%). Λ 114.6 cm2
ΩϪ1 molϪ1. IR (KBr): ν(PF6Ϫ) 835 cmϪ1. NMR (CD3NO2): δH
(200 MHz) 7.32 (2 H, m, para-H of C6H5), 6.63, 5.82 (4 H each,
both m, C6H5), 3.89, 3.39 (4 H each, both m, PCH2CH2Ph),
2.16–1.72 (36 H, m, PCCH3); δP (81.0 MHz) 98.3 (s), Ϫ142.9
[sept, J(F,P) 706.2, PF6Ϫ].
[(ꢀ6-C6H5CH2CH2PtBu2-ꢁ-P)RuCl(PMe3)]PF6 12. Method
A. A solution of 10 (92 mg, 0.16 mmol) in CH2Cl2 (8 cm3) was
treated with PMe3 (16.3 µl, 0.16 mmol) and stirred for 30 min at
room temperature. After removal of the solvent, the remaining
yellow solid was washed three times with 4 cm3 portions of
pentane, and dried in vacuo; yield 73 mg (75%).
In situ generation of [(ꢀ6-C6H5CH2CH2PtBu2-ꢁ-P)RuCl-
{O᎐C(CD ) }]PF 9. A solution of 8 (45 mg, 0.04 mmol) in
᎐
3
2
6
acetone-d6 (0.5 cm3) was stirred for 3 min at room temperature.
The NMR spectra indicated that compound 9 was generated
which, however, could not be isolated in an analytically pure
state. Careful removal of the solvent led to the re-formation of
the starting material. Spectroscopic data for 9: NMR (acetone-
d6): δH(300 MHz): 6.49 (1 H, m, C6H5), 6.06, 5.50 (2 H each,
both m, C6H5), 3.32, 2.89 (2 H each, both m, PCH2CH2Ph),
1.28 [18 H, d, J(P,H) 13.6, PCCH3]; δC (75.5 MHz) 210.5 [s,
Method B. A solution of 8 (74 mg, 0.07 mmol) in acetone
(10 cm3) was treated with PMe3 (16.3 µl, 0.16 mmol) and, after
it was stirred for 3 min at room temperature, pentane (15 cm3)
was added. A yellow solid precipitated, which was washed twice
with 5 cm3 portions of pentane, and dried in vacuo; yield 73 mg
(86%); mp 146 ЊC (decomp.) (Found: C, 36.81; H, 5.90.
C19H36ClF6P3Ru requires: C, 37.54; H, 5.97%). Λ 68.0 cm2
ΩϪ1 molϪ1. IR (KBr): ν(PF6Ϫ) 839 cmϪ1. NMR (CD2Cl2): δH
(400 MHz) 6.17, 6.09, 5.99, 5.79, 5.16 (1 H each, all m, C6H5),
3.25–3.02, 2.82–2.61 (2 H each, both m, PCH2CH2Ph), 1.78
[9 H, d, J(P,H) 10.2, PCH3], 1.40 [9 H, d, J(P,H) 14.1, PCCH3],
1.29 [9 H, d, J(P,H) 13.5, PCCH3]; δC (100.6 MHz) 123.8 (m,
ipso-C of C6H5), 104.7 (m, C6H5), 89.9 [d, J(P,C) 11.2, C6H5],
89.4 (s, C6H5), 88.4 [d, J(P,C) 10.2, C6H5], 80.0 (s, C6H5), 39.1 [d,
J(P,C) 24.4, PCH2], 37.3, 37.2 [both d, J(P,C) 13.2, PCCH3],
31.0 (s, CH2Ph), 30.7 [d, J(P,C) 4.1, PCCH3], 29.2 (br s,
PCCH3), 20.6 [d, J(P,C) 34.6, PCH3]; δP(162.0 MHz) 89.2 [d,
J(P,P) 48.0, PtBu2], Ϫ7.5 [d, J(P,P) 48.0, PMe3], Ϫ144.3 [sept,
J(F,P) 709.5, PF6Ϫ]. FAB MS (70 eV): m/z 463 (Mϩ Ϫ PF6,
11.7), 428 (Mϩ Ϫ PF6 Ϫ Cl, 1.7), 387 (Mϩ Ϫ PF6 Ϫ PMe3,
3.4%).
O᎐C(CD ) ], 115.8 (m, ipso-C of C H ), 94.6 (s, C H ), 93.1 [d,
᎐
3
2
6
5
6
5
J(P,C) 11.6, C6H5], 69.6 (s, C6H5), 38.4 [d, J(P,C) 12.7, PCCH3],
36.1 [d, J(P,C) 24.3, PCH2], 33.1 [d, J(P,C) 2.9, CH2Ph], 31.7
[sept, J(D,C) 19.5, O᎐C(CD ) ], 30.3 [d, J(P,C) 2.2, PCCH ];
᎐
3
2
3
δP (81.0 MHz) 92.5 (s), Ϫ142.7 [sept, J(F,P) 706.9, PF6Ϫ].
[(ꢀ6-C6H5CH2CH2PtBu2-ꢁ-P)RuCl(NCMe)]PF6 10. Method
A. A solution of 3 (73 mg, 0.17 mmol) in CH2Cl2 (10 cm3) and
CH3CN (5 cm3) was treated dropwise with a solution of AgPF6
(44 mg, 0.17 mmol) in CH2Cl2 (3 cm3). A gradual change of
colour from orange to yellow occurred and a white solid pre-
cipitated. After the reaction mixture was stirred for 5 min at
room temperature, the solvent was evaporated in vacuo, and the
residue was extracted twice with 5 cm3 portions of CH2Cl2. The
combined extracts were concentrated to ca. 1 cm3 in vacuo and
after addition of pentane (7 cm3) a yellow microcrystalline solid
precipitated. It was separated from the mother liquor, washed
twice with 5 cm3 portions of ether and dried; yield 73 mg (76%).
Method B. A solution of 8 (32 mg, 0.03 mmol) in acetone
(5 cm3) was treated with acetonitrile (6.3 µl, 0.12 mmol) and
stirred for 3 min at room temperature. After pentane (15 cm3)
was added, a yellow solid precipitated, which was separated
from the mother liquor, washed twice with 5 cm3 portions of
pentane and dried in vacuo; yield 33 mg (96%); mp 191 ЊC
(decomp.) (Found: C, 38.08; H, 5.16; N, 2.62. C18H30ClF6-
[(ꢀ6-C6H5CH2CH2PtBu2-ꢁ-P)RuHCl] 13. A solution of Ru-
Cl3ؒ3H2O (160 mg, 0.61 mmol) in isopropanol (8 cm3) was
treated with isoprene (2 cm3, 0.02 mol) and stirred for 6 h at
80 ЊC. A change of colour from dark green to red–brown
occurred. After cooling to room temperature the solvent was
evaporated in vacuo, the remaining light brown solid was
repeatedly washed with pentane, and dried in vacuo. The solid
(229 mg) was dissolved in THF (15 cm3), the solution was
J. Chem. Soc., Dalton Trans., 2002, 318–327
323

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treated with 1 (456 mg, 1.82 mmol) and NEt3 (85 µl, 0.61 mmol),
and the reaction mixture was stirred under a H2 atmosphere for
24 h at 75 ЊC. During that time a gradual change of colour from
brown to brown–yellow occurred. The solvent was evaporated
in vacuo, and the residue was extracted with benzene (20 cm3).
After the extract was brought to dryness in vacuo, the remaining
yellow solid was washed three times with 5 cm3 portions of
pentane, and dried in vacuo; yield 207 mg (87%). Compound 13
could also be obtained by using methanol instead of THF as
solvent. In this case the time of reaction is 20 min; yield 95%;
mp 66 ЊC (decomp.) (Found: C, 49.80, H, 6.89. C16H28ClPRu
H, vt, N 12.3, PCCH3), Ϫ16.63 [3 H, br s, RuH(H2)]; δC (50.3
MHz) 158.9 (s, ipso-C of C6H5), 129.5, 120.5, 114.7 (all s,
C6H5), 66.8 (s, CH2OPh), 35.2 (vt, N 16.6, PCCH3), 30.2 (vt, N
5.5, PCCH3), 22.0 (s, PCH2); δP (81.0 MHz) 67.2 (s).
[(C6H5OCH2CH2PtBu2-ꢁ-P)2RuHCl(CO)] 17. The gener-
ation of the intermediate, from RuCl3ؒ3H2O (196 mg, 0.75
mmol) and isoprene (4 cm3, 0.04 mol) in isopropanol (10 cm3) at
80 ЊC was carried out analogously as described for 13. The
subsequent reaction of the residue (282 mg) with 2 (599 mg,
2.25 mmol) and NEt3 (0.1 cm3, 0.75 mmol) in THF (10 cm3)
under a H2 atmosphere (1 bar) took place at 80 ЊC for 16 h.
After the reaction mixture was cooled to room temperature, the
31P NMR spectrum of the solution indicated that a mixture of
16 (ca. 40%) and 17 (ca. 60%) was formed. Therefore, the reac-
tion mixture was stirred again at 80 ЊC for 6 h but under an
argon atmosphere. An orange–yellow solution was obtained,
which after cooling was concentrated to ca. 2 cm3 in vacuo. A
yellow solid precipitated, which was filtered, washed twice with
2 cm3 portions of methanol, and dried in vacuo; yield 494 mg
(95%); mp 36 ЊC (decomp.) (Found: C, 56.46; H, 8.05.
C33H55ClO3P2Ru requires: C, 56.76; H, 7.94%). IR (KBr):
ν(RuH) 2108, ν(CO) 1906 cmϪ1. NMR (CD2Cl2): δH (400 MHz)
7.25–6.87 (10 H, m, C6H5), 4.41, 4.26 (2 H each, both m,
CH2OPh), 2.90, 2.41 (2 H each, both m, PCH2), 1.42, 1.40 (18
H each, both vt, N 12.8, PCCH3), Ϫ25.15 [1 H, t, J(P,H) 18.4,
RuH]; δC (100.6 MHz) 202.4 [t, J(P,C) 13.8, CO], 158.8 (s, ipso-
C of C6H5), 129.5, 120.7, 114.6 (all s, C6H5), 66.2 (vt, N 8.6,
CH2OPh), 36.7 (vt, N 15.3, PCCH3), 35.6 (vt, N 17.2, PCCH3),
30.8, 30.5 (both br s, PCCH3), 21.4 (vt, N 18.2, PCH2); δP (162.0
MHz) 59.0 (s).
requires: C, 49.54; H, 7.27%). IR (KBr): ν(RuH) 1990 cmϪ1
.
NMR (CD2Cl2): δH (400 MHz) 6.31, 6.20, 5.70, 5.15, 4.30 (1 H
each, all m, C6H5), 2.78–2.44 (4 H, m, PCH2CH2Ph), 1.44, 1.23
[9 H each, both d, J(P,H), 13.1, PCCH3], Ϫ7.52 [1 H, d, J(P,H)
39.2, RuH]; δC (100.6 MHz) 128.3 (s, ipso-C of C6H5), 100.0,
98.1 (both s, C6H5), 89.3 [d, J(P,C) 11.2 Hz, C6H5], 87.9 [d,
J(P,C) 6.1, C6H5], 69.9 (s, C6H5), 36.1 [d, J(P,C) 22.4, PCH2],
36.0 [d, J(P,C) 13.2, PCCH3], 34.9 [d, J(P,C) 19.3, PCCH3], 31.4
[d, J(P,C) 5.1, CH2Ph], 30.0, 28.6 [both d, J(P,C) 3.1, PCCH3];
δP (162.0 MHz) 111.8 (s).
[(ꢀ6-C6H5OCH2CH2PtBu2-ꢁ-P)RuHCl] 14. This compound
was prepared as described for 13, from RuCl3ؒ3H2O (180 mg,
0.69 mmol), isoprene (2 cm3, 0.02 mol), phosphine 2 (460 mg,
1.73 mmol), NEt3 (96 µl, 0.69 mmol) and H2 (1 bar). The
remaining residue was extracted with hexane–CH2Cl2 (5 : 1,
20 cm3) to give a yellow solid; yield 167 mg (59%); mp 46 ЊC
(decomp.) (Found C, 48.25; H, 7.17. C16H28ClOPRu requires:
C, 47.58; H, 6.99%). IR (KBr): ν(RuH) 2017 cmϪ1. NMR
(CD2Cl2): δH (300 MHz) 6.47, 6.31, 5.63, 4.95 (1 H each, all m,
C6H5), 4.28–4.13 (3 H, m, C6H5 and CH2OPh), 1.70 (2 H, m,
PCH2), 1.45 [9 H, d, J(P,H) 13.2, PCCH3], 1.25 [9 H, d, J(P,H)
12.9, PCCH3], Ϫ7.37 [1 H, d, J(P,H) 37.0, RuH]; δC (75.5 MHz)
114.6 (s, ipso-C of C6H5), 100.3, 94.1 (both s, C6H5), 89.2 [d,
J(P,C) 4.7, C6H5], 86.8 [d, J(P,C) 10.5, C6H5], 69.1 (s, C6H5),
67.8 (s, CH2OPh), 35.5 [d, J(P,C) 22.9, PCCH3], 35.1 [d, J(P,C)
14.5, PCCH3], 29.9 [d, J(P,C) 3.6, PCCH3], 27.5 [d, J(P,C) 2.5,
PCCH3], 15.8 [d, J(P,C) 20.7, PCH2]; δP (81.0 MHz) 62.6 (s).
[(C H OCH CH PtBu -ꢁ-P) Ru(CH᎐CH )Cl(CO)] 18.
A
᎐
6
5
2
2
2
2
2
slow stream of acetylene was passed for 60 s through a solution
of 17 (60 mg, 0.09 mmol) in CH2Cl2 (6 cm3) at room temper-
ature. The solution was then stirred for 3 min, the solvent was
removed in vacuo, and pentane (2 cm3) was added to the oily
residue. After storing for 6 h, an orange solid was obtained
which was washed twice with 2 cm3 portions of pentane, and
dried in vacuo; yield 55 mg (88%); mp 66 ЊC (decomp.) (Found:
C, 57.91; H, 7.72. C35H57ClO3P2Ru requires: C, 58.04; H,
[(C6H5CH2CH2PtBu2-ꢁ-P)2RuHCl(H2)] 15. The generation
of the intermediate, from RuCl3ؒ3H2O (58 mg, 0.22 mmol) and
isoprene (1 cm3, 0.01 mol) in isopropanol (5 cm3) at 80 ЊC was
carried out analogously to 13. The subsequent reaction of the
residue (84 mg) with 1 (168 mg, 0.67 mmol) and NEt3 (31 µl,
0.22 mmol) in THF (10 cm3) under a H2 atmosphere (1 bar)
took place at room temperature. After stirring the reaction mix-
ture for 60 min, an orange–brown suspension was obtained,
from which the solvent was evaporated in vacuo. The remaining
residue was extracted with pentane (25 cm3), the extract was
brought to dryness in vacuo, and the oily residue was treated
with methanol (1 cm3). An orange–yellow solid was formed,
which was filtered, washed twice with 2 cm3 portions of meth-
anol, and dried in vacuo; yield 64 mg (45%); mp 25 ЊC (decomp.)
(Found: C, 59.91; H, 8.58. C32H57ClP2Ru requires: C, 60.03; H,
8.97%). NMR (CD2Cl2): δH (300 MHz) 7.40–7.16 (10 H, m,
C6H5), 3.06, 2.18 (4 H each, both m, PCH2CH2Ph), 1.31 (36 H,
vt, N 12.3, PCCH3), Ϫ16.53 [3 H, br s, RuH(H2)]; δC (50.3
MHz) 144.3 (vt, N 12.9, ipso-C of C6H5), 128.4, 128.3, 125.8 (all
s, C6H5), 35.1 (vt, N 14.8, PCCH3), 33.6 (s, CH2Ph), 30.4 (s,
PCCH3), 25.4 (vt, N 12.9, PCH2); δP (81.0 MHz) 69.3 (s).
7.93%). IR (KBr): ν(CO) 1913, ν(C᎐C) 1599 cmϪ1. NMR
᎐
(CD2Cl2): δH (200 MHz) 7.83 [1 H, br d, J(H,H) 13.0, RuCH],
7.27–6.92 (10 H, m, C H ), 5.22 (1 H, br m, cis-H of CH᎐CH ),
᎐
6
5
2
4.82 [1 H, br d, J(H,H) 13.0, trans-H of CH᎐CH ], 4.55 (4 H,
᎐
2
m, CH2OPh), 2.82, 2.63 (2 H each, both m, PCH2), 1.25, 1.21
(18 H each, both vt, N 12.2, PCCH3); δC (50.3 MHz) 180.9 (br
m, CO), 158.9 (s, ipso-C of C6H5), 151.8 (br m, RuCH), 129.5
(s, C H ), 122.0 (s, CH᎐CH ), 120.6, 114.6 (both s, C H ), 64.6
᎐
6
5
2
6
5
(s, CH2OPh), 37.8, 37.7 (both vt, N 13.1, PCCH3), 31.0, 30.4
(both s, PCCH3), 22.9 (vt, N 15.3, PCH2); δP (81.0 MHz) 40.1
(s). FAB MS (70 eV): m/z 724 (Mϩ, 0.4), 689 (Mϩ Ϫ Cl, 0.4%).
[(C6H5OCH2CH2PtBu2-ꢁ-P)2RuHF(CO)] 19. A solution of
17 (102 mg, 0.15 mmol) in acetone (10 cm3) was treated with
CsF (130 mg, 0.86 mmol) and stirred for 24 h at room temper-
ature. The solvent was removed in vacuo, and the residue was
extracted twice with 5 cm3 portions of pentane. The combined
extracts were brought to dryness in vacuo, and the pale-yellow
residue was recrystallized from pentane (2 cm3) at Ϫ60 ЊC; yield
61 mg (60%). (Found: C, 56.79; H, 7.72. C33H55FO3P2Ru
requires: C, 58.13; H, 8.13%). IR (KBr): ν(RuH) 2102, ν(CO)
1898 cmϪ1. NMR (CD2Cl2): δH (200 MHz) 7.21–6.86 (10 H, m,
C6H5), 4.48, 4.30 (2 H each, both m, CH2OPh), 2.58, 2.27 (2 H
each, both m, PCH2), 1.39, 1.38 (18 H each, both vt, N 13.0,
PCCH3), Ϫ24.20 [1 H, dt, J(F,H) 2.2, J(P,H) 18.0, RuH]; δC
(100.6 MHz) 205.5 (m, CO), 158.8 (s, ipso-C of C6H5), 129.5,
120.6, 114.6 (all s, C6H5), 66.2 [dvt, N 8.6, J(F,C) 4.3, CH2OPh],
36.2 (vt, N 15.3, PCCH3), 35.1 (vt, N 17.2, PCCH3), 30.2 (br s,
PCCH3), 30.0 (vt, N 4.8, PCCH3), 21.1 (vt, N 16.2, PCH2);
[(C6H5OCH2CH2PtBu2-ꢁ-P)2RuHCl(H2)] 16. This com-
pound was prepared as described for 15, from RuCl3ؒ3H2O (88
mg, 0.34 mmol), isoprene (2 cm3, 0.02 mol), phosphine 2 (270
mg, 1.01 mmol), NEt3 (47 µl, 0.34 mmol) and H2 (1 bar).
Orange solid: yield 124 mg (53%); mp 22 ЊC (decomp.) (Found:
C, 56.91; H, 8.08. C32H57ClO2P2Ru requires: C, 57.17; H,
8.54%). NMR (CD2Cl2): δH (300 MHz) 7.30–6.89 (10 H, m,
C6H5), 4.43 (4 H, m, CH2OPh), 2.38 (4 H, m, PCH2), 1.28 (36
324
J. Chem. Soc., Dalton Trans., 2002, 318–327

View Article Online
δP (81.0 MHz) 62.1 [d, J(F,P) 21.8]; δF (188.3 MHz) Ϫ203.0
[t, J(P,F) 21.8 Hz].
propyn-1-ol (42 mg, 0.20 mmol) in acetone (7 cm3) was treated
dropwise with a solution of AgPF6 (39 mg, 0.15 mmol) in acet-
one (5 cm3). After the reaction mixture was stirred for 5 min at
room temperature, the solution was filtered, and the filtrate was
brought to dryness in vacuo. The residue was dissolved in
CH2Cl2 (15 cm3), and the solution was filtered with Celite.
After the solvent was evaporated from the filtrate, the remain-
ing violet solid was repeatedly washed with pentane and dried
in vacuo; yield 85 mg (80%); mp 94 ЊC (decomp.) (Found: C,
51.85; H, 5.49. C31H37ClF6P2Ru requires: C, 51.56; H, 5.16%).
[(C6H5OCH2CH2PtBu2-ꢁ-P)2RuHCl(CO)2] 20. Method A. A
slow stream of CO was passed for 60 s through a suspension of
17 (51 mg, 0.07 mmol) in hexane (5 cm3) at room temperature.
A colourless solution was formed, of which the solvent was
removed in vacuo. The off-white residue was washed twice with
2 cm3 portions of pentane, and dried in vacuo; yield 50 mg
(95%).
Method B. The generation of the intermediate, from RuCl3ؒ
3H2O (47 mg, 0.18 mmol) and isoprene (1 cm3, 0.01 mol) in
isopropanol (5 cm3) at 80 ЊC was carried out analogously to
13. The subsequent reaction of the residue (69 mg) with 2 (146
mg, 0.55 mmol) and NEt3 (26 µl, 0.18 mmol) in methanol (10
cm3) under a H2 atmosphere (1 bar) took place at 70 ЊC for 30
min. After the reaction mixture was cooled to room tempera-
ture, a slow stream of CO was passed through the solution for
45 s. A change of colour from orange–yellow to pale yellow
was observed. The solution was concentrated to ca. 2 cm3 in
vacuo, which led to the precipitation of an off-white solid. It
was filtered, washed three times with 3 cm3 portions of metha-
nol, and dried in vacuo; yield 75 mg (56%); mp 110 ЊC
(decomp.) (Found: C, 55.77; H, 7.33. C34H55ClO4P2Ru
requires: C, 56.22; H, 7.63%). IR (KBr): ν(RuH) 2041, ν(CO)
1965, 1925 cmϪ1. NMR (CD2Cl2): δH (400 MHz) 7.28–6.92 (10
H, m, C6H5), 4.53, 4.39 (2 H each, both m, CH2OPh), 2.78,
2.49 (2 H each, both m, PCH2), 1.48 (36 H, vt, N 11.4,
PCCH3), Ϫ5.51 [1 H, t, J(P,H) 19.7, RuH]; δC (100.6 MHz)
201.1 [t, J(P,C) 13.4, CO], 200.1 [t, J(P,C) 6.2, CO], 158.8 (s,
ipso-C of C6H5), 129.5, 120.7, 114.6 (all s, C6H5), 65.7 (vt, N
5.7, CH2OPh), 37.1 (vt, N 20.0, PCCH3), 36.9 (vt, N 16.2,
PCCH3), 30.6, 29.9 (both s, PCCH3), 21.3 (vt, N 19.1, PCH2);
δP (162.0 MHz) 65.8 (s).
Λ (CH3NO2) 54.0 cm2 ΩϪ1 molϪ1. IR (KBr): ν(C᎐C᎐C) 1972,
᎐ ᎐
ν(PF6Ϫ) 840 cmϪ1. NMR (CD2Cl2): δH (300 MHz) 8.04–7.50
(10 H, m, C6H5), 6.89, 6.64, 6.50, 6.08, 5.61 (1 H each, all m,
η6-C6H5), 3.27–2.84, 2.31–2.17 (2 H each, both m, PCH2-
CH2Ph), 1.52 [9 H, d, J(P,H) 14.3, PCCH3], 1.15 [9 H, d, J(P,H)
14.9, PCCH3]; δC (75.5 MHz) 285.2 [d, J(P,C) 17.1, Ru᎐C],
᎐
178.5, 172.0 (both s, ᎐C᎐CPh ), 142.0 (s, ipso-C of C H ), 135.2,
᎐ ᎐
2
6
5
133.9, 129.6 (all s, C6H5), 120.5 [d, J(P,C) 5.2, ipso-C of
η6-C6H5], 111.9, 103.7 (both s, η6-C6H5), 101.5 [d, J(P,C) 4.7,
η6-C6H5], 95.3 [d, J(P,C) 8.8, η6-C6H5], 86.8 (s, η6-C6H5), 39.1
[d, J(P,C) 14.5, PCH2], 38.1 [d, J(P,C) 10.9, PCCH3], 37.8 [d,
J(P,C) 3.1, PCCH3], 32.2 (s, CH2Ph), 29.8, 28.9 (both s,
PCCH3); δP (81.0 MHz) 113.6 (s, PtBu2), Ϫ143.9 [sept, J(F,P)
711.2, PF6Ϫ].
[(ꢀ6-C H OCH CH PtBu -ꢁ-P)RuCl(᎐C᎐C᎐CPh )]PF
᎐ ᎐ ᎐
6
23.
6
5
2
2
2
2
This compound was prepared as described for 22b, from 4 (67
mg, 0.15 mmol), 1,1-diphenyl-2-propyn-1-ol (34 mg, 0.16 mmol)
and AgPF6 (39 mg, 0.15 mmol) in acetone (12 cm3). Violet
solid: yield 74 mg (67%); mp 66 ЊC (decomp.) (Found: C, 50.12;
H, 5.23. C31H37ClF6OP2Ru requires: C, 50.45; H, 5.05%). Λ
(CH3NO2) 64.4 cm2 ΩϪ1 molϪ1. IR (KBr): ν(C᎐C᎐C) 1970,
᎐ ᎐
ν(PF6Ϫ) 841 cmϪ1. NMR (CD2Cl2): 7.81–7.27 (10 H, m, C6H5),
6.60, 6.45, 6.09, 6.01, 5.41 (1 H each, all m, η6-C6H5), 4.84–4.49
(2 H, m, CH2OPh), 2.39–1.89 (2 H, m, PCH2), 1.53 [9 H, d,
J(P,H) 14.2, PCCH3], 1.14 [9 H, d, J(P,H) 14.6, PCCH3]; δH
(81.0 MHz) 64.7 (s, PtBu2), Ϫ144.0 [sept, J(F,P) 712.0, PF6Ϫ].
[(C6H5OCH2CH2PtBu2-ꢁ-P)2RuHF(CO)2] 21. A solution of
20 (62 mg, 0.09 mmol) in acetone (8 cm3) was treated with CsF
(100 mg, 0.66 mmol) and stirred for 24 h at room temperature.
The solvent was removed in vacuo, and the residue was
extracted twice with 6 cm3 portions of pentane. The combined
extracts were brought to dryness in vacuo, the remaining yellow
solid was washed twice with 2 cm3 portions of pentane (Ϫ78 ЊC)
and dried in vacuo; yield 55 mg (87%); mp 117 ЊC (Found: C,
56.96; H, 7.85. C34H55FO4P2Ru requires: C, 57.53; H, 7.81%).
IR (KBr): ν(RuH) 2048, ν(CO) 1975, 1910 cmϪ1. NMR
(CD2Cl2): δH (400 MHz) 7.24–6.88 (10 H, m, C6H5), 4.44 (4 H,
m, CH2OPh), 2.49, 2.40 (2 H each, both m, PCH2), 1.46 (36 H,
vt, N 12.2, PCCH3), Ϫ4.31 [1 H, dt, J(F,H) 7.6, J(P,H) 19.8,
RuH]; δC (100.6 MHz) 203.1 [dt, J(F,C) 66.8, J(P,C) 11.9, CO],
200.1 [dt, J(F,C) 6.7, J(P,C) 6.7, CO], 158.8 (s, ipso-C of C6H5),
129.5, 120.5, 114.5 (all s, C6H5), 66.0 [dvt, N 7.6, J(F,C) 3.8,
CH2OPh], 36.4, 36.3 (both vt, N 18.1, PCCH3), 30.3, 29.9 (both
s, PCCH3), 20.8 [dvt, N 18.1, J(F,C) 3.8, PCH2]; δP (162.0 MHz)
71.9 [d, J(F,P) 20.3]; δF (376.5 MHz) Ϫ395.2 [t, J(P,F) 20.3].
[(C H CH CH PtBu -ꢁ-P) RuHCl(᎐C᎐CH )] 24.
᎐ ᎐
A slow
6
5
2
2
2
2
2
stream of acetylene was passed for 10 s through a cooled sol-
ution (Ϫ78 ЊC) of 15 (54 mg, 0.08 mmol) in CH2Cl2 (5 cm3). A
change of colour from orange to red–brown occurred. The
solvent was evaporated in vacuo, the orange–brown residue was
washed twice with 2 cm3 portions of pentane (0 ЊC), and dried
in vacuo; yield 53 mg (95%); mp 58 ЊC (decomp.) (Found: C,
61.40; H, 8.71. C34H57ClP2Ru requires: C, 61.48; H. 8.65%). IR
(KBr): ν(RuH) 2106, ν(C᎐C) 1601 cmϪ1. NMR (CD2Cl2): δH
᎐
(300 MHz) 7.16 (10 H, m, C6H5), 3.18, 2.95 (2 H each, both m,
PCH CH Ph), 2.63 [2 H, t, J(P,H) 3.5, ᎐CH ], 2.50, 2.13 (2 H
᎐
2
2
2
each, both m, PCH2CH2Ph), 1.42, 1.39 (18 H each, both vt, N
12.3, PCCH3), Ϫ15.80 [1 H, t, J(P,H) 18.0, RuH]; δC (75.5
MHz) 326.5 [t, J(P,C) 15.1, Ru᎐C], 142.7 (vt, N 13.0, ipso-C of
᎐
C6H5), 127.7, 127.4, 125.2 (all s, C6H5), 87.9 [t, J(P,C) 3.4,
᎐CH ], 36.9 (vt, N 13.5, PCCH ), 35.7 (vt, N 14.0, PCCH ), 32.9
᎐
2
3
3
(s, CH2Ph), 30.3 (vt, N 4.7, PCCH3), 29.6 (vt, N 4.2, PCCH3),
22.4 (vt, N 17.7, PCH2); δP (81.0 MHz) 53.7 (s).
[(ꢀ6-C H CH CH PtBu -ꢁ-P)RuCl(᎐C᎐C᎐CPh )]BF 22a. A
᎐ ᎐ ᎐
6
5
2
2
2
2
4
solution of 13 (127 mg, 0.33 mmol) and 1,1-diphenyl-2-propyn-
1-ol (75 mg, 0.36 mmol) in acetone (10 cm3) was treated drop-
wise at Ϫ78 ЊC with a solution of HBF4 in ether (0.2 cm3,
0.32 mmol). After stirring for 2 min, the reaction mixture
was warmed to room temperature, and then the solvent was
removed in vacuo. A violet solid was obtained, which was
washed three times with 5 cm3 portions of pentane, and dried in
vacuo; yield 207 mg (94%); mp 68 ЊC (decomp.) (Found: C,
56.10; H, 6.60. C31H37BClF4PRu requires: C, 56.08; H, 5.62%).
[(C H OCH CH PtBu -ꢁ-P) RuHCl(᎐C᎐CH )] 25. This
᎐ ᎐
6
5
2
2
2
2
2
compound was prepared as described for 24, from 16 (109 mg,
0.16 mmol) and acetylene in CH2Cl2 (8 cm3) at Ϫ78 ЊC. Light
brown solid: yield 98 mg (88%); mp 58 ЊC (decomp.) (Found:
C, 58.61; H, 8.07. C34H57ClO2P2Ru requires: C, 58.65; H,
8.25%). IR (KBr): ν(RuH) 2085, ν(C᎐C) 1600 cmϪ1. NMR
᎐
(CD2Cl2): δH (300 MHz) 7.21–6.76 (10 H, m, C6H5), 4.31 (4 H,
m, CH OPh), 2.64 [2 H, t, J(P,H) 3.7, ᎐CH ], 2.58, 2.31 (2 H
᎐
2
2
Λ (CH3NO2) 49.5 cm2 ΩϪ1 molϪ1. IR (KBr): ν(C᎐C᎐C) 1970,
each, both m, PCH2), 1.35, 1.31 (18 H each, both vt, N 12.8,
PCCH3), Ϫ14.85 [1 H, t, J(P,H) 18.5, RuH]; δC (75.5 MHz)
᎐ ᎐
ν(BF4Ϫ) 1056 cmϪ1
.
328.1 [t, J(P,C) 15.1, Ru᎐C], 159.6 (s, ipso-C of C H ), 130.2,
121.4, 115.3 (all s, C H ), 90.0 [t, J(P,C) 3.9, ᎐CH ], 67.7 (vt,
᎐
6 5 2
᎐
6
5
[(ꢀ6-C H CH CH PtBu -ꢁ-P)RuCl(᎐C᎐C᎐CPh )]PF 22b. A
᎐ ᎐ ᎐
6
5
2
2
2
2
6
suspension of 3 (65 mg, 0.15 mmol) and 1,1-diphenyl-2-
N 8.3, CH2OPh], 38.6 (vt, N 14.8, PCCH3), 37.2 (vt, N 15.2,
J. Chem. Soc., Dalton Trans., 2002, 318–327 325

View Article Online
Table 3 Crystallographic data for 10 and 17
Formula
M
C18H30ClF6NP2Ru (10)
572.90
C33H55ClO3P2Ru (17)
698.26
Crystal system
Space group
a/Å
b/Å
c/Å
α/Њ
β/Њ
Monoclinic
P21/c (no. 14)
11.204(2)
12.920(3)
15.626(3)
90.0
90.24(3)
90.0
2261.9(8)
173(2)
Triclinic
P1 (no. 2)
¯
11.676(2)
12.255(3)
13.537(3)
79.57(3)
68.26(3)
82.44(3)
1765.1(6)
173(2)
γ/Њ
V/Å3
T /K
Z
4
2
Dc/g cmϪ3
λ(Mo-Kα)/Å
µ/mmϪ1
1.682
0.71073
1.007
1.314
0.71073
0.640
No. of reflections measured
23880
4006
0.0353
0.0968
16057
5845
0.0509
0.1464
No. of unique reflections
R1a
wR2b
Residual electron density/e ÅϪ3
0.030/Ϫ0.029
1.924/Ϫ0.567
2
2
a R = Σ|Fo Ϫ Fc|/ΣFo [for I > 2σ(I )] for the number of observed reflections, respectively. b wR2 = [Σw(Fo2 Ϫ Fc2)2/Σw(Fo )2]1/2; wϪ1 = [σ2(Fo ) ϩ (0.0507P)2
ϩ 0.0128P] (10), [σ2(Fo ) ϩ (0.1062P)2 ϩ 0.0000P] (17), where P = [Fo2 ϩ 2Fc2]/3; for all data reflections, respectively.
2
PCCH3), 31.5 (vt, N 4.6, PCCH3), 30.8 (vt, N 4.2, PCCH3),
21.8 (vt, N 19.0, PCH2); δP (81.0 MHz) 50.5 (s).
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft (SFB 347)
and the Fonds der Chemischen Industrie for financial support,
In situ generation of [(C6H5CH2CH2PtBu2-ꢁ-P)2RuHCl-
the latter in particular for a Ph. D. grant (to K. I.). We are also
grateful to Mrs R. Schedl and Mr C. P. Kneis (DTA measure-
ments and elemental analyses), to Mrs M.-L. Schäfer and
Dr W. Buchner (NMR spectra), and to Dr G. Lange and
Mr F. Dadrich (mass spectra). The experimental assistance of
Mr S. Stellwag is also gratefully acknowledged.
᎐
(᎐CCH )(OEt )]BF 26. A solution of 24 (40 mg, 0.06 mmol) in
᎐
3
2
4
CD2Cl2 (0.5 cm3) was treated at Ϫ78 ЊC with a slight excess of a
1.6 M solution of HBF4 in ether (50 µl, 0.08 mmol). After the
solution was warmed to ca. 0 ЊC, the 1H and 31P NMR spectra
were measured. NMR (CD2Cl2): δH (200 MHz) 7.29–6.80
᎐
(10 H, m, C H ), 3.06 (4 H, m, CH Ph), 2.64 (3 H, s, Ru᎐CCH ),
᎐
6
5
2
3
2.45 (4 H, m, PCH2), 1.46 (36 H, m, PCCH3), Ϫ7.63 [1 H, t,
J(P,H) 15.6, RuH]; δP (81.0 MHz) 68.3 (s).
References
General procedure for studying the catalytic activity for ROMP
of the vinylidene and carbene ruthenium complexes
1 R. H. Grubbs, S. J. Miller and G. C. Fu, Acc. Chem. Res., 1995, 28,
446; T. M. Trnka and R. H. Grubbs, Acc. Chem. Res., 2001, 34, 18;
R. H. Grubbs and S. Chang, Tetrahedron, 1998, 54, 4413; S. K.
Armstrong, J. Chem. Soc., Perkin Trans. 1, 1998, 371; A. Fürstner,
Top. Organomet. Chem., 1998, 1, 37; A. Fürstner, Top. Catal., 1997,
4, 285; M. Schuster and S. Blechert, Angew. Chem., 1997, 109, 2124;
M. Schuster and S. Blechert, Angew. Chem., Int. Ed. Engl., 1997, 36,
2036; K. J. Ivin and J. C. Mol, Olefin Metatheses and Metatheses
Polymerization, Academic Press, New York, 1997.
An NMR tube was filled stepwise with cyclooctene (81.4 µl,
625 µmol) and a 1.6 M solution of HBF4 in diethyl ether (2.5 µl,
4 µmol). To this mixture, a solution of compound 24 or 25
(0.5 µmol) or of the Grubbs carbene [RuCl (᎐CHPh)(PCy ) ]
᎐
2
3 2
(0.5 µmol) in CD2Cl2 (0.5 cm3) was added. The solution was
shaken for 10–20 s, and then the increase in concentration of
the polymer was followed by 1H NMR spectroscopy. For 24 as
the catalyst, the amount of trans-olefinic bonds in the polymer
was 69%, and for 25 as the catalyst 50%.
2 Representative articles: E. L. Dias and R. H. Grubbs,
Organometallics, 1998, 17, 2758; S. Chang, L. Jones, C. Wang, L. M.
Henling and R. H. Grubbs, Organometallics, 1998, 17, 3460; M. S.
Sanford, L. M. Henling and R. H. Grubbs, Organometallics, 1998,
17, 5384; S. M. Hansen, M. A. O. Volland, F. Rominger, F.
Eisenträger and P. Hofmann, Angew. Chem., 1999, 111, 1360;
S. M. Hansen, M. A. O. Volland, F. Rominger, F. Eisenträger and
P. Hofmann, Angew. Chem., Int. Ed., 1999, 38, 1273; S. M. Hansen,
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Crystallography
Single crystals of 10 were grown from dichloromethane at room
temperature, those of 17 from dichloromethane–pentane at
Ϫ78ЊC. Crystal data collection parameters are summarized in
Table 3. Intensity data were corrected for Lorentz and polaris-
ation effects for 10 and 17. Data reduction was performed with
Stoe IPDS software. An absorption correction could not be
applied, and therefore large residual electron densities result.
The structures were solved by direct methods (SHELXS-97).26
For 10 the counterion PF6 was found disordered (F3–F6) and
refined anisotropically without restraints (occupancy factors
69/31); moreover, twin refinement was necessary [BASF =
0.141(1)]. For 17 the hydrido ligand could not be located.
Atomic coordinates and anisotropic thermal displacement
parameters of the non-hydrogen atoms were refined aniso-
tropically by full-matrix least squares on F 2 (SHELXL-97).26
CCDC reference numbers 175267 and 175268.
See http://www.rsc.org/suppdata/dt/b1/b106243n/ for crystal-
lographic data in CIF or other electronic format.
326
J. Chem. Soc., Dalton Trans., 2002, 318–327

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