Vinylidene transition-metal complexes, 50([≠] carbynehydrido- and vinylidenehydridoosmium complexes with Os(PCy3)2 as a molecular unit

Article abstract of DOI:10.1002/(sici)1099-0682(199906)1999:6<951::aid-ejic951>3.0.co;2-u

The reaction of OsCl₃·2H₂O with PCy₃ leads under reducing conditions either to [OsH₆(PCy₃)₂] (1) or [OsH₂Cl₂(PCy₃)₂] (2). Treatment of 2 with ter

Full text of DOI:10.1002/(sici)1099-0682(199906)1999:6<951::aid-ejic951>3.0.co;2-u

FULL PAPER
Vinylidene Transition-Metal Complexes, 50[°]
Carbynehydrido- and Vinylidenehydridoosmium Complexes with Os(PCy3)2
as a Molecular Unit
Helmut Werner,*[a] Stefan Jung,[a] Birgit Weberndörfer,[a] and Justin Wolf[a]
Dedicated to Professor Christoph Elschenbroich on the occasion of his 60th birthday
Keywords: Osmium / Alkynes / Carbyne complexes / Hydrido complexes / Vinylidene complexes
The reaction of OsCl3·2H2O with PCy3 leads under reducing
conditions either to [OsH6(PCy3)2] (1) or [OsH2Cl2(PCy3)2]
(2). Treatment of 2 with terminal alkynes HCϵCR (R = Ph,
SiMe3) affords the carbynehydrido complexes [OsHCl2-
(ϵCCH2R)(PCy3)2] (4, 5), of which 5 (R = SiMe3) is easily
converted with traces of water into [OsHCl2(ϵCCH3)(PCy3)2]
(6). Compound 4 (R = Ph) reacts with NaOMe to yield the
vinylidenehydridoosmium(II) complex [OsHCl(=C=CHPh)-
(PCy3)2] (7) which upon treatment with HBF4/OEt2 gives the
five-coordinate cationic species [OsHCl(ϵCCH2Ph)(PCy3)2]-
BF4 (8). The reaction of [OsH3Cl(PCy3)2] (9) with HCϵCC-
(CH3)2Cl affords
a mixture of [OsHCl2(ϵCCH=CMe2)-
(PCy3)2] (10) and [OsCl2(H2)(=CHCH=CMe2)(PCy3)2] (11).
Compound 11 is quite labile and by elimination of H2 gives
10. The molecular structure of 10 has been determined by X-
ray crystallography.
In the course of our continuous studies on the synthesis pounds [RuCl2(ϭCHR)(PCy3)2] afford the isomeric carby-
and reactivity of vinylidenemetal complexes with d6- and nehydrido complexes [OsHCl2(ϵCR)(PCy3)2] in good
d8-metal centers,[1] we recently reported that the reaction of yields in the case of osmium. While these six-coordinate
the ruthenium(IV) compound [RuH2Cl2(PiPr3)2] with ter- compounds are quite stable and inert towards olefins, the
minal alkynes HCϵCR led, depending on the conditions, five-coordinate cationic complex [OsHCl(ϵCCH2Ph)-
to the formation not only of the expected vinylidene com- (PCy3)2]BF4 is catalytically active and catalyzes the ring-
plexes [RuCl2(ϭCϭCHR)(PiPr3)2] but also of the related opening metathesis polymerization (ROMP) of cyclopen-
carbene derivatives [RuCl2(ϭCHCH2R)(PiPr3)2].[2] Since tene.
compounds of this type, in particular with PCy3 instead of
PiPr3 as P-donor ligand, proved to be excellent catalysts for
olefin metathesis (including RCM and ROMP),[3] we be-
came interested in studying the formation of carbene com-
Results and Discussion
plexes [RuCl2(ϭCHCH2R)(PRЈ3)2] from Ru-containing
precursors and HCϵCR in more detail. As a consequence
Dihydrido- and Polyhydridoosmium Complexes
we developed a convenient and very efficient one-pot syn-
thesis of compounds [RuCl2(ϭCHCH2R)(PCy3)2] (R ϭ H,
Ph) from ruthenium trichloride, PCy3, Mg, H2, water, and
terminal alkynes as starting materials.[4] The principal ad-
vantage of this method is that it avoids expensive precursors
such as [RuCl2(PPh3)3],[5] [Ru(η4-C8H12)(η6-C8H10)],[6] or
[RuH2(H2)2(PCy3)2],[7] and uses alkynes instead of cyclo-
propenes, diazoalkanes, vinyl chlorides, or propargylic chlo-
rides as carbene sources.
The aim of the present work was to find out whether the
osmium counterparts to the Grubbs-type carbeneruthen-
ium complexes are equally accessible and if so, what their
catalytic activity is. Here we report that the preparative
routes which for ruthenium give the five-coordinate com-
Under the conditions under which RuCl3 · 3 H2O is
converted into the hydrido(dihydrogen) complex
[RuHCl(H2)(PCy3)2],[4] the reaction of OsCl3 · 2 H2O with
activated Mg and PCy3 under H2 takes a different course.
After the suspension in THF was stirred for 4 h at 65°C, a
mixture of products was formed in which, besides two un-
known compounds, the dihydridoosmium(IV) complex 2
1
(Scheme 1) could be identified by H- and 31P-NMR spec-
troscopy. The trihydrido derivative [OsH3Cl(PCy3)2], the
generation of which was anticipated in analogy to that of
[RuHCl(H2)(PCy3)2], could not be detected. If the reaction
mixture formed from OsCl3 · 2 H2O was continuously
stirred under H2 at 85°C for 19 h, an off-white solid precipi-
tated from which upon extraction with CH2Cl2 the hexahy-
drido complex [OsH6(PCy3)2] (1) was isolated. The prep-
aration of this compound was previously reported by Hal-
pern et al.[8] who treated (NH4)2[OsCl6] with PCy3 and
NaBH4 in the presence of ethanol. The new synthetic route
described here is more efficient and has the advantage of
[°] Part 49: J. Gil-Rubio, B. Weberndörfer, H. Werner, J. Chem.
Soc., Dalton Trans., submitted.
[a]
Institut für Anorganische Chemie der Universität Würzburg,
Am Hubland, D-97074 Würzburg, Germany
Eur. J. Inorg. Chem. 1999, 951Ϫ957
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1434Ϫ1948/99/0606Ϫ0951 $ 17.50ϩ.50/0
951

H. Werner, S. Jung, B. Weberndörfer, J. Wolf
FULL PAPER
the starting material OsCl3 · 2 H2O instead of the more ex- Carbyne- and Vinylideneosmium Complexes
pensive (NH4)2[OsCl6].
We recently reported that the ruthenium counterpart of
compound 2 with the composition [RuH2Cl2(PCy3)2],
which was prepared by Chaudret et al. from
[RuH2(H2)2(PCy3)2] and aqueous HCl in ether[11] and inde-
pendently by us from [RuHCl(H2)(PCy3)2],[12] reacts with
phenylacetylene to give the five-coordinate vinylidene com-
plex [RuCl2(ϭCϭCHPh)(PCy3)2].[12] In contrast, treatment
of 2 with three equivalents of HCϵCPh in hexane at 60°C
affords instead of [OsCl2(ϭCϭCHPh)(PCy3)2] the six-coor-
dinate carbynehydrido compound 4 in 63% yield of isolated
product. The analogous reaction of 2 with HCϵCSiMe3
leads to a mixture of two products 5 and 6, of which the
first is by far the most dominant species (Scheme 2). The
31P-NMR spectrum of the freshly isolated yellow solid dis-
plays a rather strong singlet at δ ϭ 11.2 and a weaker reson-
ance at δ ϭ 10.8, which we assign to compounds 5 and 6,
Scheme 1
The above-mentioned dihydridoosmium(IV) complex
[OsH2Cl2(PCy3)2] (2) is accessible from OsCl3 · 2 H2O and
PCy3 in 2-propanol under reflux conditions. The same pro-
cedure had already been applied in our laboratory to afford
the related species [OsH2Cl2(L)2] with L ϭ PiPr3 and
PtBu2Me, which represented the first examples of hexacoor-
dinate osmium(IV) dihydrides.[9] Compound 2 was also ob-
tained in almost quantitative yield on treatment of 1 with
gaseous HCl in hexane. The most typical spectroscopic fea-
tures of 2 (which is a red-brown, moderately air-sensitive
solid) is the singlet for the two phosphane ligands in the
31P-NMR spectrum at δ ϭ 33.6 and the triplet for the OsH2
protons in the 1H-NMR spectrum at δ ϭ Ϫ15.68. Based on
the analogy of these spectroscopic data to those of
[OsH2Cl2(PiPr3)2], we assume that the structure of 2 is simi-
lar to that of the bis(triisopropylphosphane) derivative,
which is best described as a square antiprism with two miss-
ing vertexes.[9]
1
respectively. In the hydride region of the H-NMR spec-
trum of the mixture of 5 and 6 two triplets appear, the
chemical shifts and the P-H coupling constants of which
are only slightly different. Compound 5 containing the
CH2SiMe3-substituted carbyne is completely converted into
6 upon addition of two drops of H2O to a solution in
CD2Cl2. Therefore, we assume that the small quantities of
the carbyne complex 6 formed in the reaction of 2 with
HCϵCSiMe3 in hexane originate from traces of water in
the reaction system. Besides the hydride resonance in the
1H-NMR spectrum, a characteristic spectroscopic feature
for 5 and 6 is the signal of the carbyne carbon atom in the
13C-NMR spectrum which appears at δ ϭ 267.6 (5) and
265.5 (6), respectively. The corresponding resonance for 4
is observed at δ ϭ 265.8.
The reaction of 1 with hydrogen chloride deserves a spe-
cial comment. If a slow stream of HCl is passed through a
suspension of 1 in hexane, almost instantaneously a floccu-
lent white precipitate is formed which, after the reaction
mixture is stirred for 10Ϫ15 min, is converted into the red-
brown compound 2. When the treatment of the starting ma-
terial with HCl is stopped after ca. 30 s and the flocculent
precipitate separated from the solution, we observed that
the color of the off-white solid changed to brown. The 31P-
NMR spectrum of the freshly isolated intermediate dis-
played, besides the signals of 1 and 2 at δ ϭ 45.0 and 33.6,
a third singlet at δ ϭ 13.1, which we tentatively assign to
the dichlorotetrahydridoosmium(VI) complex 3 (Scheme 1).
Scheme 2
1
The H-NMR spectrum of the crude product supports this
proposal since it shows in the high-field region a signal at
With regard to the mechanism of formation of 4 and 5,
δ ϭ Ϫ10.16 which due to P-H coupling is split into a triplet. we assume that the starting material 2, containing a metal
Recently, Berke et al. reported the preparation of the corre- center with a 16-electron configuration, generates in the in-
sponding triisopropylphosphane derivative [OsH4Cl2- itial step of the reaction a 1:1 adduct with the alkyne. It is
(PiPr3)2], the 1H-NMR spectrum of which displays a reson- conceivable that this seven-coordinate species is in equilib-
2
ance at δ ϭ Ϫ10.55 with a J(PH) coupling constant of rium with the (dihydrogen)osmium(II) compound
1
10.1 Hz.[10] We note that even if the H-NMR spectrum of [OsCl2(H2)(HCϵCR)(PCy3)2], which could first rearrange
the intermediate is measured in CD2Cl2 at Ϫ78°C, a slow to the isomeric vinylidene derivative [OsCl2(H2)(ϭCϭ
evolution of gas (H2) takes place accompanied by the con- CHR)(PCy3)2] and finally by intramolecular hydrogen
version of compound 3 to the more stable dichlorodihydri- transfer to [OsHCl2(ϵCCH2R)(PCy3)2]. A similar reaction
doosmium(IV) complex 2.
scheme has been proposed by Esteruelas and Oro et al.,
952
Eur. J. Inorg. Chem. 1999, 951Ϫ957

Vinylidene Transition-Metal Complexes, 50
FULL PAPER
who prepared analogous carbynehydridoosmium complexes by a solvent molecule. By taking the molecular structure of
with two triisopropylphosphane ligands from [OsH2Cl2- compound 10 (see below) and of the cationic carbyne com-
(PiPr3)2] and HCϵCR.[13] A different synthetic route lead- plex [OsH{ϵCCHϭC(CH3)2}(κ2-O2CCH3)(PiPr3)2]ϩ into
ing to [OsHCl2(ϵCCH2R)(PiPr3)2] was most recently re- consideration,[19] we assume that in 8 the coordination
ported by Caulton and co-workers, who used instead of 1- around the metal center corresponds to that of a square
alkynes the corresponding alkenes CH2ϭCHR as starting pyramid with the carbyne moiety in the apical position. In
1
materials.[14] There is ample precedence for this water-as- agreement with this proposal, the H-NMR spectrum of 8
sisted conversion of 5 into 6, as we[15] as well as others[13a,16] displays a resonance for the hydrido ligand at δ ϭ Ϫ8.75
observed that upon treatment of various low-valent tran- and the 13C-NMR spectrum exhibits a signal for the car-
sition-metal compounds with silylated alkynes or diynes in byne carbon atom at δ ϭ 279.6, the latter of which is split
the presence of traces of H2O or HX, metal complexes with into a triplet due to P-C coupling. For the related bis(triiso-
CϪH instead of CϪSiR3 bonds are formed.
propylphosphane) complex [OsHCl(ϵCCH2Ph)(PiPr3)2]ϩ,
The six-coordinate carbynehydrido complex 4 reacts with which was most recently isolated by Spivak and Caulton
NaOMe in THF to give the five-coordinate vinylidenehydri- with [{3,5-(CF3)2C6H3}4B]Ϫ as the anion, the chemical
doosmium(II) compound 7 in 87% isolated yield. The re- shifts for the hydride and the carbyne carbon resonances
lated bis(triisopropylphosphane) complex had been pre- are δ ϭ Ϫ9.84 and 282.6, respectively.[20]
1
pared on a similar route.[13b] The H-NMR spectrum of 7
The synthesis of neutral six-coordinate carbynehydri-
(which is a deep green, moderately air-sensitive solid) exhib- doosmium(II) compounds is also possible by using propar-
its in the high-field region a triplet at δ ϭ Ϫ16.38 which is gylic chlorides instead of 1-alkynes such as HCϵCPh or
typical for species of this type.[12][13] The presence of the HCϵCSiMe3 as substrates. In this case, the starting mate-
vinylidene ligand is indicated by the 13C-NMR resonances rial 2 was first converted into [OsH3Cl(PCy3)2] (9), which
at δ ϭ 282.8 and 107.3, which are assigned to the α- and β- was obtained from 2 and 2-propanol in the presence of
carbon atoms of the OsϭCϭCHR chain. Since the 31P- NEt3 as a brown-yellow air-sensitive solid in almost quanti-
NMR spectrum of 7 displays a singlet at δ ϭ 26.6, we as- tative yield (Scheme 4). The counterparts of 9 with PiPr3
sume, in agreement with theoretical studies by Eisenstein, and PtBu2Me as phosphane ligands were recently prepared
Caulton et al.[17], that for the five-coordinate hydridovinyli- along a similar route.[17][21] Each of the three compounds
dene compound a distorted trigonal-bipyramidal geometry of the general composition [OsH3Cl(PR3)2] is fluxional in
1
is most likely.
solution. The H-NMR spectrum of 9 (in CD2Cl2) displays
a broad singlet at δ ϭ Ϫ19.22 at 25°C, which upon cooling
the solution to 0°C is split into a triplet. Below Ϫ23°C, a
new broadening of the hydride signal is observed which,
however, is not resolved even at Ϫ60°C. Caulton and co-
workers reported that the spectrum of [OsH3Cl(PiPr3)2]
shows AB2 patterns in the hydride region below Ϫ80°C.[21a]
Scheme 3
The reactivity of compound 7 resembles that of the ru-
thenium counterpart [RuHCl(ϭCϭCH2)(PCy3)2].[18] If
HBF4 is used as the substrate, the attack of the proton does
not occur at the metal but at the β-carbon atom of the Osϭ
CϭCHPh unit and thus converts the vinylidene into a car-
byne ligand (Scheme 3). In contrast to [RuHCl(ϵCCH3)(O-
Et2)(PCy3)2]BF4, which is rather labile and decomposes in
CH2Cl2 at room temperature within 20Ϫ30 min,[18] the os-
mium complex 8 is considerably more stable. In the solid
state, it can be stored under argon at 25°C for days, and in
solution (CD2Cl2) at Ϫ18°C it does not decompose within
Scheme 4
24 h.
The reaction of 9 with 3-chloro-3-methylbut-1-yne in di-
1
The elemental analysis as well as the H-NMR spectrum chloromethane at Ϫ40°C gives a mixture of two products.
confirm that in 8, unlike in [RuHCl(ϵCCH3)(S)(PCy3)2]ϩ The more labile component is the carbene(dihydrogen) de-
(S
ϭ
OEt2, OH2)[18] and [OsHCl(ϵCCH2Ph)(OH2)- rivative 11 (see Scheme 4), which could not be separated
(PiPr3)2]ϩ,[13b] the open coordination site is not occupied from the mixture and was therefore characterized by H-
1
Eur. J. Inorg. Chem. 1999, 951Ϫ957
953

H. Werner, S. Jung, B. Weberndörfer, J. Wolf
FULL PAPER
and 13C-NMR spectroscopy. Compound 11 reacts upon Catalytic Studies
warming to 25°C to afford the carbynehydrido complex 10,
It was recently found in our laboratory[18] that the cat-
ionic carbynehydridoruthenium complexes [RuHCl-
(ϵCCH3)(S)(PCy3)2]BF4 (S ϭ OEt2, OH2) are highly ef-
ficient catalysts for olefin metathesis. They are not only
more active than the Grubbs compound [RuCl2(ϭ
CHPh)(PCy3)2] in the ring-opening metathesis polymeri-
zation (ROMP) of cyclooctene but, even more remarkably,
they also catalyze the cross-olefin metathesis of cyclopen-
tene with methyl acrylate. By this novel route, a homolo-
gous series of multiply unsaturated esters is formed. For the
neutral carbyneruthenium complexes [RuCl(ϵCR)(CO)-
(PPh3)2], prepared by Roper et al.,[24] a similar catalytic ac-
tivity is unkown.[25]
which was isolated as a pale brownish solid in 53% yield.
The most typical spectroscopic features in the 1H-NMR
spectrum for 10 are, besides the resonances for the hydrido
ligand and the carbyne carbon atom, the signals for the
ϭCH proton at δ ϭ 4.39 and for the inequivalent ϭCMe2
methyl protons at δ ϭ 2.01 and 1.50. The resonances for
the ϭCH and ϭCMe2 carbon nuclei appear in the 13C-
NMR spectrum at δ ϭ 135.9 and 162.1.
The result of the X-ray crystal structure analysis of 10 is
shown in Figure 1. The coordination geometry around the
osmium center can be described as a distorted octahedron
with the two phosphane ligands in the apical positions. The
carbyne unit is disposed trans to one of the two chlorides.
Both the C1ϪOsϪCl2 and P1ϪOsϪP2 axes are slightly
bent, the bond angle P1ϪOsϪP2 [167.95(3)°] in 10 being
somewhat larger than in the non-hydride-containing
derivative [OsCl2(ϵCCHϭCPh2)(κ1-P-iPr2PCH2CO2Me)-
{κ2-P,O-iPr2PCH2C(O)O}] [165.0(1)°], which was recently
prepared in our laboratory.[22] The OsϪC1 distance in 10
According to these results, it is not surprising that under
standard conditions[5e] neither 4 nor 10 is catalytically ac-
tive in ROMP of cyclopentene. However, the cationic spe-
cies 8 reacts rather smoothly in CH2Cl2 with this olefin.
After 24 h at room temperature, a highly viscous material
was generated from which, after it was dissolved in CHCl3
and the solution poured into methanol, a white powder
could be obtained in about 40% yield. The comparison of
˚
[1.715(4) A] is nearly identical to that in the above-men-
[22]
˚
tioned carbyne complex [1.72(1) A]
as well as in the tri-
1
the H- and 13C-NMR data of the polymer with those re-
isopropylphosphane
(PiPr3)2] [1.711(4) A].
derivative
[OsHCl2(ϵCCH2Ph)-
˚
ported in the literature[25] revealed that 77% of the double
bonds are trans-configured. The turnover frequency was de-
termined as 154.2 hϪ1 at 25°C. To the best of our knowl-
edge, compound 8 is the first well-defined osmium complex
which catalyzes ROMP of cyclopentene.[25] We note that
[13a]
There is, however, a significant
difference between the OsϪC bond length in 10 and in
[23]
˚
[OsCl(ϵCC6H4Me-4)(CO)(PPh3)2] [1.78(2) A]
which
could be explained by the different oxidation state and co-
ordination number of the two compounds. The C1ϪC2 and
C2ϪC3 bond lengths in 10 are in the expected range and
this is true also for the OsϪP distances.
OsCl3 · x H2O, an adduct of osmium chloride and cyclo-
[25]
octa-1,5-diene,[26] and also OsO4
were found to be cata-
lytically active in olefin metathesis but as far as we know
not in ROMP of cyclopentene.
Experimental Section
All operations were carried out under argon with Schlenk tech-
niques. The alkynes and PCy3 were commercial products from
Strem and ABCR. Ϫ NMR: Bruker AC 200 and AMX 400 [vt ϭ
virtual triplet; N ϭ 1J(PC) ϩ 3J(PC)]. Ϫ Melting points determined
by DTA.
1. Preparation of [OsH6(PCy3)2] (1): To
a slurry of 0.5 g
(20.6 mmol) of magnesium turnings, which were activated with 0.50
mL of 1,2-C2H4Cl2, in 25 mL of THF was added stepwise 2.23 g
(7.80 mmol) of PCy3 and 557 mg (1.70 mmol) of OsCl3 · 2 H2O.
The reaction mixture was heated under vigorous stirring under H2
(1 bar) for 90 min at 65°C and then for 19 h at 85°C. After the
mixture was cooled to room temperature, the solution was sepa-
rated from the solid (mainly Mg) and the solvent was removed in
vacuo. The residue was dissolved in 30 mL of CH2Cl2 and 10 mL
of H2O. The organic layer was separated, concentrated to dryness
in vacuo, and the residue washed twice with 15-mL portions of 2-
propanol and dried. The remaining white solid was identified as 1
Figure 1. Molecular structure (ORTEP plot) of 10;[a] the carbon
atoms of the cyclohexyl rings are reduced in size for clarity; selected
˚
bond lengths [A] and angles [°]: OsϪC1 1.715(4), OsϪP1 2.417(1),
1
by comparison of the H- and 31P-NMR data with those reported
OsϪP2 2.422(1), OsϪCl1 2.515(1), OsϪCl2 2.488(1), C1ϪC2
1.434(5), C2ϪC3 1.364(5), C3ϪC4 1.480(6), C3ϪC5 1.490(5);
P1ϪOsϪP2 167.95(3), P1ϪOsϪC1 90.9(1), P1ϪOsϪCl1 95.42(3),
P1ϪOsϪCl2 88.24(3), P2ϪOsϪC1 91.0(1), P2ϪOsϪCl1 95.87(3),
P2ϪOsϪCl2 87.76(3), C1ϪOsϪCl1 101.0(1), C1ϪOsϪCl2
in the literature;[8] yield 742 mg (58%).
2. Preparation of [OsH2Cl2(PCy3)2] (2): a) A suspension of 611 mg
(1.87 mmol) of OsCl3 · 2 H2O in 2 mL of 2-propanol was treated
with a solution of 2.76 g (9.85 mmol) of PCy3 in 20 mL of 2-propa-
nol and then heated for 24 h under reflux. After the reaction mix-
170.0(1),
Cl1ϪOsϪCl2
89.02(4),
OsϪC1ϪC2
174.4(3),
C1ϪC2ϪC3 120.6(4), C2ϪC3ϪC4 124.1(4), C2ϪC3ϪC5 119.5(3),
C4ϪC3ϪC5 116.3(3)
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Vinylidene Transition-Metal Complexes, 50
FULL PAPER
ture was cooled to room temperature, a red-brown solid precipi-
tated. The solid was separated from the mother liquor, washed
twice with 10-mL portions of methanol (0°C), twice with 10-mL
portions of ether (0°C) and dried in vacuo; yield 1.21 g (79%). Ϫ
tities of toluene and pentane (both 0°C) and dried; yield 163 mg
(87%); m.p. 131°C. Ϫ H NMR (400 MHz, C6D6): δ ϭ 7.56Ϫ6.78
1
(m, 5 H, C6H5), 2.66 (br. s, 1 H, ϭCHPh), 2.21Ϫ1.18 (m, 66 H,
C6H11), Ϫ16.38 [t, J(PH) ϭ 13.0 Hz, 1 H, OsH]. Ϫ 13C NMR
b) A slow stream of dry HCl was passed through a suspension of (100.6 MHz, C6D6): δ ϭ 284.1 [t, J(PC) ϭ 9.5 Hz, OsϭC], 128.3,
86 mg (0.11 mmol) of 1 in 8 mL of hexane for 30 s at room tem- 128.1, 123.4, 122.8 (all s, C6H5), 108.6 (s, OsϭCϭC), 36.1 (vt, N ϭ
perature. A dark brown solution was formed from which, after it 22.9 Hz, ipso-C of C6H11), 30.9, 30.6 (both s, m-C of C6H11), 28.1,
had been stirred for 10 min, a red-brown solid precipitated. The
mother liquor was separated and the residue was washed with 5 mL
27.9 (both vt, N ϭ 10.2 Hz, o-C of C6H11), 26.9 (s, p-C of C6H11).
Ϫ
of hexane and dried; yield 90 mg (96%); m.p. 94°C. Ϫ 1H NMR Ϫ C44H73ClOsP2 (889.7): calcd. C 59.40, H 8.27; found C 59.07,
(400 MHz, C6D6): δ ϭ 2.28Ϫ1.15 (m, 66 H, C6H11), Ϫ15.68 [t, H 7.87.
31P NMR (162.0 MHz, C6D6): δ ϭ 26.6 [s, J(OsP) ϭ 181.4 Hz].
J(PH) ϭ 35.1 Hz, 2 H, OsH2]. Ϫ 13C NMR (100.6 MHz, C6D6):
7. Preparation of [OsHCl(ϵCCH2Ph)(PCy3)2]BF4 (8): A solution
δ ϭ 39.9 [d, J(PC) ϭ 30.5 Hz, ipso-C of C6H11], 30.0 (s, m-C of
of 244 mg (0.27 mmol) of 7 in 40 mL of toluene was treated drop-
C6H11), 27.8 [d, J(PC) ϭ 10.2 Hz, o-C of C6H11], 26.9 (s, p-C of
wise with 2 mL of a 1.4  solution (2.8 mmol) of HBF4 in ether.
C6H11). Ϫ 31P NMR (162.0 MHz, C6D6): δ ϭ 33.6 (s). Ϫ
A rapid change of color from deep green to brown-yellow took
C36H68Cl2OsP2 (824.0): calcd. C 52.48, H 8.32; found C 52.26, H
place. After the reaction mixture had been stirred for 10 min at
8.24.
room temperatuere, a pale brownish solid precipitated which was
3. Preparation of [OsHCl2(ϵCCH2Ph)(PCy3)2] (4): A suspension
of 393 mg (0.48 mmol) of 2 in 18 mL of hexane was treated with of toluene and dried; yield 112 mg (43%); m.p. 134°C (dec.). Ϫ H
separated from the mother liquor, washed twice with 8-mL portions
1
156 µL (1.42 mmol) of phenylacetylene and stirred for 24 h at
60°C. A pale brownish solid precipitated. After the reaction mix-
ture was cooled to room temperature, the mother liquor was sepa-
rated, the solid residue was washed twice with 5-mL portions of
hexane and dried; yield 282 mg (63%); m.p. 129°C. Ϫ 1H NMR
NMR (400 MHz, CD2Cl2): δ ϭ 7.36Ϫ7.05 (m, 5 H, C6H5), 3.01 (s,
2 H, CH2), 2.39Ϫ1.17 (m, 66 H, C6H11), Ϫ8.75 (br. s, 1 H, OsH).
Ϫ
13C NMR (100.6 MHz, CD2Cl2): δ ϭ 279.6 [t, J(PC) ϭ 10.8 Hz,
OsϵC], 130.1, 129.2, 129.0, (all s, C6H5), 57.1 (s, CH2), 36.3 (vt,
N ϭ 25.4 Hz, ipso-C of C6H11), 30.6, 30.1 (both s, m-C of C6H11),
(400 MHz, CD2Cl2): δ ϭ 7.45Ϫ7.25 (m, 5 H, C6H5), 2.61 (s, 2 H, 27.6, 27.4 (both vt, N ϭ 10.2 Hz, o-C of C6H11), 26.3 (s, p-C of
CH2Ph), 2.33Ϫ1.04 (m, 66 H, C6H11), Ϫ6.64 [t, J(PH) ϭ 16.8 Hz, 1
H, OsH]. Ϫ 13C NMR (100.6 MHz, CD2Cl2): δ ϭ 265.8 [t, J(PC) ϭ
11.5 Hz, OsϵC], 129.5, 129.1, 128.8, 128.1 (all s, C6H5), 56.9 (s,
CH2Ph), 36.8 (br. s, ipso-C of C6H11), 29.9, 29.4 (both s, m-C of
C6H11), 27.9 (br. s, o-C of C6H11), 27.0 (s, p-C of C6H11). Ϫ 31P
NMR (162.0 MHz, CD2Cl2): δ ϭ 8.8 [s, J(OsP) ϭ 169.6 Hz]. Ϫ
C44H74Cl2OsP2 (926.1): calcd. C 57.06, H 8.05; found C 56.58, H
7.97.
C6H11). Ϫ 31P NMR (162.0 MHz, CD2Cl2): δ ϭ 46.3 (br. s). Ϫ
C44H74BClF4OsP2 (977.5): calcd. C 54.07, H 7.63; found C 53.61,
H 7.77.
8. Preparation of [OsH3Cl(PCy3)2] (9): A suspension of 89 mg
(0.11 mmol) of 2 in 5 mL of 2-propanol was treated with 38 µL
(0.27 mmol) of NEt3 and stirred for 2 h at room temperature. A
change of color from red-brown to brown-yellow occurred. The
solvent was removed in vacuo and the residue was dissolved in
10 mL of benzene. The solution was filtered and the filtrate was
concentrated to dryness in vacuo. The remaining brown-yellow
4. Preparation of [OsHCl2(ϵCCH2SiMe3)(PCy3)2] (5): A suspen-
sion of 307 mg (0.37 mmol) of 2 in 15 mL of hexane was treated
with 156 µL (1.10 mmol) of HCϵCSiMe3 and stirred for 6 h at solid was repeatedly washed with methanol and dried; yield 75 mg
60°C. A yellow solid precipitated which was isolated as described (86%); m.p. 40°C (dec.). Ϫ 1H NMR (400 MHz, C6D6, 25°C): δ ϭ
for 4; yield 178 mg. The NMR spectra of the isolated product indi-
cated that besides 5 also small amounts of 6 were already formed. NMR (200 MHz, CD2Cl2, 0°C): δ ϭ 2.10Ϫ1.21 (m, 66 H, C6H11),
2.31Ϫ1.15 (m, 66 H, C6H11), Ϫ19.22 (br. s, 3 H, OsH3). Ϫ 1H
Typical data for 5: 1H NMR (400 MHz, CD2Cl2): δ ϭ 0.06 (s,
SiMe3), Ϫ7.64 [t, J(PH) 17.6 Hz, OsH].
13C NMR
(100.6 MHz, CD2Cl2): δ ϭ 267.6 (br. s, OsϵC), 30.5 (s, CH2). Ϫ
31P NMR (162.0 MHz, CD2Cl2): δ ϭ 11.2 (s).
Ϫ19.74 [t, J(PH) ϭ 11.5 Hz, 3 H, OsH3]. Ϫ 13C NMR (100.6 MHz,
C6D6, 25°C): δ ϭ 37.4 (vt, N ϭ 23.4 Hz, ipso-C of C6H11), 31.0 (s,
m-C of C6H11), 28.0 (vt, N ϭ 10.2 Hz, o-C of C6H11), 27.0 (s, p-C
of C6H11). Ϫ 31P NMR (162.0 MHz, C6D6, 25°C): δ ϭ 41.8 (s). Ϫ
31P NMR (81.0 MHz, CD2Cl2, 0°C): δ ϭ 41.8 (s). Ϫ C36H69ClOsP2
(789.5): calcd. C 54.77, H 8.81; found C 55.22, H 8.64.
ϭ
Ϫ
5. Preparation of [OsHCl2(ϵCCH3)(PCy3)2] (6): A suspension of
220 mg (0.27 mmol) of 2 in 15 mL of hexane was treated with 112
µL (0.79 mmol) of HCϵCSiMe3 and a few drops of water and then
9. Reaction of Compound 9 with 3-Chloro-3-methylbut-1-yne: A
stirred for 24 h at 60°C. A pale brownish solid precipitated, which solution of 57 mg (0.07 mmol) of 9 in 0.5 mL of CD2Cl2 was
was isolated as described for 4; yield 136 mg (60%); m.p. 152°C. Ϫ
treated at Ϫ40°C in an NMR tube with 8.5 µL (0.18 mmol) of
1H NMR (400 MHz, CD2Cl2): δ ϭ 2.40Ϫ1.30 (m, 66 H, C6H11), HCϵCC(CH3)2Cl. The NMR spectra of the solution indicated the
0.94 (s, 3 H, CH3), Ϫ7.31 [t, J(PH) ϭ 16.8 Hz, 1 H, OsH]. Ϫ 13C formation of a mixture of 10 and 11 which could not be separated
NMR (100.6 MHz, CD2Cl2): δ ϭ 265.5 [t, J(PC) ϭ 11.5 Hz,
OsϵC], 38.6 (s, CH3), 35.7 (br. s, ipso-C of C6H11), 29.9, 29.5 (both
s, m-C of C6H11), 28.1, 27.9 (both vt, N ϭ 10.2 Hz, o-C of C6H11),
by fractional crystallization. Therefore, the more labile component
11 was characterized by NMR spectroscopy. Typical data for 11:
1H NMR (400 MHz, CD2Cl2, Ϫ70°C): δ ϭ 16.88 [d, J(HH) ϭ
27.1 (s, p-C of C6H11). Ϫ 31P NMR (162.0 MHz, CD2Cl2): δ ϭ 12.7 Hz, 1 H, OsϭCH], 7.03 [d, J(HH) ϭ 12.7 Hz, 1 H, CHϭ
10.8 [s, J(OsP) ϭ 167.9 Hz]. Ϫ C38H70Cl2OsP2 (850.0): calcd. C CMe2], 2.95Ϫ0.77 (m, 72 H, C6H11 and CH3], Ϫ7.52 [br. s, 2 H,
53.69, H 8.30; found C 53.62, H 8.38.
Os(H2)]. Ϫ 13C NMR (100.6 MHz, CD2Cl2, Ϫ70°C): δ ϭ 254.9
(br. s, OsϭC). Ϫ 31P NMR (162.0 MHz, CD2Cl2, Ϫ70°C): δ ϭ
Ϫ1.1 (br. s). Ϫ 31P NMR (81.0 MHz, CD2Cl2, Ϫ40°C): δ ϭ 1.2 (s).
6. Preparation of [OsHCl(؍C؍CHPh)(PCy3)2] (7): A suspension
of 208 mg (0.23 mmol) of 4 in 35 mL of THF was treated with
14.6 mg (0.27 mmol) of NaOMe and stirred for 2 h at room tem-
perature. After the solvent was removed, the residue was extracted
with 20 mL of toluene. The extract was concentrated to dryness in
vacuo, and the remaining green solid was washed with small quan-
10. Preparation of [OsHCl2(ϵCCH؍CMe2)(PCy3)2] (10): The solu-
tion, obtained from 9 and HCϵCC(CH3)2Cl as described above,
was stirred after warming for 1 h at room temperature. The solvent
was removed, the remaining pale brownish solid was washed with
Eur. J. Inorg. Chem. 1999, 951Ϫ957
955

H. Werner, S. Jung, B. Weberndörfer, J. Wolf
FULL PAPER
[3c]
1
2036Ϫ2055. Ϫ
A. S. K. Hashmi, J. Prakt. Chem. 1997, 339,
A. Fürstner, Top. Catal. 1997, 4, 285Ϫ299.
2 mL of hexane and dried; yield 34 mg (53%); m.p. 122°C. Ϫ H
NMR (400 MHz, CD2Cl2): δ ϭ 4.39 (s, 1 H, CHϭCMe2),
2.36Ϫ1.15 (m, 66 H, C6H11), 2.01 (s, 3 H, CH3 trans to ϭCH), 1.50
(s, 3 H, CH3 cis to ϭCH), Ϫ7.17 [t, J(PH) ϭ 17.6 Hz, 1 H, OsH].
[3d]
195Ϫ199. Ϫ
[4]
J. Wolf, W. Stüer, C. Grünwald, H. Werner, P. Schwab, M.
Schulz, Angew. Chem. 1998, 110, 1165Ϫ1167; Angew. Chem.
Int. Ed. Engl. 1998, 37, 1124Ϫ1126.
[5] [5a]
Ϫ
13C NMR (100.6 MHz, CD2Cl2): δ ϭ 256.0 [t, J(PC) ϭ 11.4 Hz,
S. T. Nguyen, L. K. Johnson, R. H. Grubbs, J. Am. Chem.
[5b]
Soc. 1992, 114, 3974Ϫ3975. Ϫ
G. C. Fu, S. T. Nguyen, R.
OsϵC], 162.1 (s, ϭCMe2), 135.9 (s, ϭCH), 36.5 (br. vt, N ϭ
11.4 Hz, ipso-C of C6H11), 29.6, 29.3 (both s, m-C of C6H11), 28.2,
28.0 (both vt, N ϭ 5.1 Hz, o-C of C6H11), 27.1 (s, p-C of C6H11),
26.4, 23.6 (both s, CH3). Ϫ 31P NMR (162.0 MHz, CD2Cl2): δ ϭ
8.2 [s, J(OsP) ϭ 169.6 Hz]. Ϫ C41H74Cl2OsP2 (890.1): calcd. C
55.33, H 8.38; found C 55.16, H 8.16.
[5c]
H. Grubbs, J. Am. Chem. Soc. 1993, 115, 9856Ϫ9857. Ϫ
S.
T. Nguyen, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1993,
115, 9858Ϫ9859. Ϫ [5d] P. Schwab, M. B. France, J. W. Ziller, R.
H. Grubbs, Angew. Chem. 1995, 107, 2179Ϫ2181; Angew. Chem.
[5e]
Int. Ed. Engl. 1995, 34, 2039Ϫ2041. Ϫ
P. Schwab, R. H.
Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1996, 118, 100Ϫ110. Ϫ
[5f]
D. M. Lynn, S. Kanaoka, R. H. Grubbs, J. Am. Chem. Soc.
1996, 118, 784Ϫ790.
11. ROMP of Cyclopentene with Compound 8 as Catalyst: A solu-
tion of 30 mg (0.03 mmol) of 8 in 1 mL of CH2Cl2 was treated with
10 mL (0.11 mol) of cyclopentene and stirred for 24 h at room
temperature. The highly viscous reaction mixture was dissolved in
40 mL of CHCl3 and the solution was poured into 100 mL of
methanol. The white material was filtered and, after it was dried
in vacuo, characterized by 1H- and 13C-NMR spectroscopy. The
comparison of the NMR data with those reported in the litera-
ture[25] revealed a trans/cis ratio of the configuration at the double
bonds of 77:23; yield 4.19 g.
[6]
[7]
T. R. Belderrain, R. H. Grubbs, Organometallics 1997, 16,
4001Ϫ4003.
[7a] M. L. Christ, S. Sabo-Etienne, B. Chaudret, Organometallics
1994, 13, 3800Ϫ3804. Ϫ [7b] M. Olivan, K. G. Caulton, J. Chem.
´
Soc., Chem. Commun. 1997, 1733Ϫ1734.
[8]
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P. J. Desrosiers, L. Cai, Z. Lin, R. Richards, J. Halpern, J. Am.
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[10]
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D. G. Gusev, V. F. Kuznetsov, I. L. Eremenko, H. Berke, J. Am.
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12. Determination of the X-ray Crystal Structure of 10:[27] Single
crystals of 10 were grown from CH2Cl2. Crystal data (from 5000
reflections, 4.26° < Θ < 54.06°): monoclinic; space group I2/a (No.
[12]
J. Wolf, W. Stüer, C. Grünwald, O. Gevert, M. Laubender, H.
Werner, Eur. J. Inorg. Chem. 1998, 1827Ϫ1834.
˚
15); a ϭ 25.655(5), b ϭ 9.527(2), c ϭ 39.988(8) A, β ϭ 107.26(3)°;
[13] [13a]
J. Espuelas, M. A. Esteruelas, F. J. Lahoz, L. A. Oro, N.
3
V ϭ 9333(3) A ; Z ϭ 8; dcalcd. ϭ 1.448 gcmϪ3; µ(Mo-Kα) ϭ 3.115
˚
[13b]
Ruiz, J. Am. Chem. Soc. 1993, 115, 4683Ϫ4689. Ϫ
M.
mmϪ1; crystal size 0.13 ϫ 0.12 ϫ 0.10 mm; STOE (IPDS), Mo-Kα
Bourgault, A. Castillo, M. A. Esteruelas, E. On˜ate, N. Ruiz,
˚
radiation (0.71073 A), graphite monochromator; T ϭ 173(2) K; ψ-
Organometallics 1997, 16, 636Ϫ645.
[14]
´
G. J. Spivak, J. N. Coalter, M. Olivan, O. Eisenstein, K. G.
scans, max. 2Θ ϭ 54.06°; 82743 reflections measured, 10147 inde-
pendent (Rint. ϭ 0.0303), 7230 with I > 2σ(I). Intensity data were
corrected for Lorentz and polarization effects. The structure was
solved by direct methods (SHELXS-86).[28] Atomic coordinates
and the anisotropic thermal parameters of non-hydrogen atoms
were refined by full-matrix least squares on F2 (SHELXL-93).[29]
The positions of all hydrogen atoms, except of metal-bound H,
were calculated according to ideal geometry and refined by using
the riding method. The position of H could be located in a final
difference Fourier synthesis and was refined with fixed Ueq. The
asymmetric unit includes one and a half molecules of CH2Cl2
which were refined anisotropically. Two alternative positions for
CH2Cl2 consisting of C91, Cl5, and Cl6 were found and refined
with the occupancy factors 0.54:0.46 with restraints. Conventional
R ϭ 0.0313 [for 7230 reflections with I > 2σ(I)], and weighted
wR2 ϭ 0.0682 for all 10137 located reflections; reflection/parameter
Caulton, Organometallics 1998, 17, 999Ϫ1001.
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A. Höhn, H. Otto, M. Dziallas, H. Werner, J. Chem. Soc.,
[15b]
Chem. Commun. 1987, 852Ϫ854. Ϫ
A. Höhn, H. Werner,
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1359Ϫ1364. Ϫ
ganomet. Chem. 1993, 451, 175Ϫ182. Ϫ
Baum, D. Schneider, B. Windmüller, Organometallics 1994, 13,
H. Werner, D. Schneider, M. Schulz, J. Or-
[15f]
H. Werner, M.
[15g]
1089Ϫ1097. Ϫ
H. Werner, R. W. Lass, O. Gevert, J. Wolf,
Organometallics 1997, 16, 4077Ϫ4088.
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M. Olivan, E. Clot, O. Eisenstein, K. G. Caulton, Organomet-
[17]
´
allics 1998, 17, 897Ϫ901.
[18]
[19]
[20]
W. Stüer, J. Wolf, H. Werner, P. Schwab, M. Schulz, Angew.
Chem. 1998, 110, 3603Ϫ3606; Angew. Chem. Int. Ed. Engl.
1998, 37, 3421Ϫ3423.
Ϫ3
˚
ratio 21.12; residual electron density ϩ2.401/Ϫ1.213 eA
.
´
P. Crochet, M. A. Esteruelas, A. M. Lopez, M.-P. Martinez, M.
´
Olivan, E. On˜ate, N. Ruiz, Organometallics 1998, 17,
4500Ϫ4509.
Acknowledgments
G. J. Spivak, K. G. Caulton, Organometallics 1998, 17,
5260Ϫ5266.
[21] [21a]
This work was supported by the Deutsche Forschungsgemeinschaft
(SFB 347) and the Fonds der Chemischen Industrie. We thank Dr.
W. Buchner and Mrs. M.-L. Schäfer for NMR spectra, and Mrs.
R. Schedl and Mr. C. P. Kneis for elemental analyses and DTA
measurements. Generous support by the BASF AG and the De-
gussa AG (gifts of chemicals) is also gratefully acknowledged.
D. Gusev, R. Kuhlman, G. Sini, O. Eisenstein, K. G. Caul-
[21b]
ton, J. Am. Chem. Soc. 1994, 116, 2685Ϫ2686. Ϫ
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K. G. Caulton, J. Am. Chem. Soc. 1997, 119, 10153Ϫ10169.
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C. Grünwald, O. Gevert, J. Wolf, P. Gonzalez-Herrero, H.
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956
Eur. J. Inorg. Chem. 1999, 951Ϫ957

Vinylidene Transition-Metal Complexes, 50
FULL PAPER
[27]
[28]
[29]
Crystallographic data (excluding structure factors) for the struc-
G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467.
G. M. Sheldrick, A program for crystal structure refinement,
University of Göttingen, 1993.
tures reported in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary publi-
cation no. CCDC-114480. Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK (Fax: internat. ϩ44-1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk).
Received February 16, 1999
[I99053]
Eur. J. Inorg. Chem. 1999, 951Ϫ957
957