Synthesis and molecular structure of six-coordinate dichlorodihydridoruthenium(IV) and five-coordinate vinylideneruthenium(II) complexes

Article abstract of DOI:10.1002/(SICI)1099-0682(199811)1998:11<1827::AID-EJIC1827>3.0.CO;2-Q

The dichlorodihydridoruthemum(IV) compound [RuH₂Cl₂(PiPr₃)₂] (4) was prepared from [RuCl₂(C₈H₁₂)]_n, (3), PiPr₃, and H₂ in 2-butanol via the chlorohydridoruthenium(II) derivative [RuHCl(H₂)(PiPr₃)₂] (5) as an intermediate. The synthesis of 5 was achieved under similar conditions from 3, PiPr₃, H₂, and 2-butanol in the presence of NEt₃. Compound 4, which was characterized by X-ray crystal structure analysis, reacts with excess phenylacetylene to give the phenylvinylidene complex [RuCl₂(=C=CHPh)(PiPr₃)₂] (7) and with propargylic alcohols or derivatives thereof to afford the vinylcarbene complexes [RuCl₂(=CHCH=CR₂)(PiPr₃)₂] (9, 10), respectively. From 5 and terminal alkynes RC≡CH the chlorohydndovinylidene compounds [RuHCl(=C=CHR)(PiPr₃)₂] (11, 12) were obtained. The phenylvinylidene complex [RuCl₂(=C= CHPh)(PCy₃)₂] (15) was prepared from phenylacetylene and either [RuH₂Cl₂(PCy₃)₂] (14) or one of the carbcne derivatives [RuCl₂(=CHR)(PCy₃)₂] (16, 17) as starting materials. The X-ray crystal structure analysis of 15 confirms a distorted square-pyramidal geometry with the vinylidene ligand in the apical position. The interconversion of 4 to 5 and of the tricyclohexylphosphane counterparts 14 to 13 was achieved by hydrogen transfer from 2-propanol in the presence of PR₃. The reverse reaction occurs upon treatment of 5 or 13 with the corresponding phosphonium salt [HPR₃]Cl or HCl, respectively.

Full text of DOI:10.1002/(SICI)1099-0682(199811)1998:11<1827::AID-EJIC1827>3.0.CO;2-Q

FULL PAPER
Vinylidene Transition-Metal Complexes, 47[᭛]
Synthesis and Molecular Structure of Six-Coordinate
Dichlorodihydridoruthenium(IV) and Five-Coordinate Vinylideneruthenium(II)
ComplexesȠ
Justin Wolf, Wolfram Stüer, Claus Grünwald, Olaf Gevert, Matthias Laubender, and Helmut Werner*
Institut für Anorganische Chemie der Universität Würzburg,
Am Hubland, D-97074 Würzburg, Germany
Received August 6, 1998
Keywords: Ruthenium / Terminal alkynes / Carbene complexes / Hydrido complexes / Vinylidene complexes
The dichlorodihydridoruthenium(IV) compound [RuH2Cl2-
(PiPr3)2] (4) was prepared from [RuCl2(C8H12)]n (3), PiPr3, and
H2 in 2-butanol via the chlorohydridoruthenium(II) derivative
[RuHCl(H2)(PiPr3)2] (5) as an intermediate. The synthesis of
5 was achieved under similar conditions from 3, PiPr3, H2,
and 2-butanol in the presence of NEt3. Compound 4, which
was characterized by X-ray crystal structure analysis, reacts
with excess phenylacetylene to give the phenylvinylidene
complex [RuCl2(=C=CHPh)(PiPr3)2] (7) and with propargylic
alcohols or derivatives thereof to afford the vinylcarbene
complexes [RuCl2(=CHCH=CR2)(PiPr3)2] (9, 10), respectively.
From 5 and terminal alkynes RCϵCH the chlorohydrido-
vinylidene compounds [RuHCl(=C=CHR)(PiPr3)2] (11, 12)
were obtained. The phenylvinylidene complex [RuCl2(=C=
CHPh)(PCy3)2] (15) was prepared from phenylacetylene and
either [RuH2Cl2(PCy3)2] (14) or one of the carbene deriva-
tives [RuCl2(=CHR)(PCy3)2] (16, 17) as starting materials. The
X-ray crystal structure analysis of 15 confirms a distorted
square-pyramidal geometry with the vinylidene ligand in the
apical position. The interconversion of 4 to 5 and of the
tricyclohexylphosphane counterparts 14 to 13 was achieved
by hydrogen transfer from 2-propanol in the presence of PR3.
The reverse reaction occurs upon treatment of 5 or 13 with
the corresponding phosphonium salt [HPR3]Cl or HCl,
respectively.
In the course of our investigations aimed to prepare bis- the analogous compound [RuH2Cl2(PtBu2Me)2] using our
(trialkylphosphane) transition-metal complexes containing methodology with the cycloocta-1,5-diene derivative 3 as
coordinatively unsaturated metal centers, we recently de- the starting material.[6]
scribed the synthesis of the dichlorodihydridoosmium(IV)
In this article we describe the preparation and charac-
compounds [OsH2Cl2(PiPr3)2] (1) and [OsH2Cl2- terization of 4 and its PCy3 counterpart 13, and the use of
(PtBu2Me)2] (2), in which osmium, although six-coordinate, these dichlorodihydridoruthenium(IV) compounds as well
has 16 electrons in its valence shell.[1] These compounds, in as of the related chlorohydrido(dihydrogen)ruthenium(II)
particular 1, have a rich chemistry which has opened the derivatives to obtain five-coordinate vinylideneru-
gate not only to carbyne- but also to vinylideneosmium thenium(II) complexes. Part of these studies has been com-
complexes.[2][3]
municated.[5]
Since it was known from our work on the reactivity of
compounds such as [MCl2{κ2(P,O)-iPr2PCH2CH2OMe}2]
and [MCl2{κ2(P,O)-iPr2PCH2CO2R}2] (M ϭ Ru, Os) that
the ruthenium derivatives react more readily with terminal
alkynes and propargylic alcohols to give the corresponding
vinylidene and allenylidene complexes,[4] we set out to pre-
pare the hitherto unknown ruthenium(IV) compound
[RuH2Cl2(PiPr3)2] (4). After initial attempts with RuCl3 ·aq
as starting material failed, we found that the reaction of
[RuCl2(C8H12)]n (3) with triisopropylphosphane in 2-buta-
nol under H2 gave the dichlorodihydrido complex 4.[5] Most
recently, Caulton and coworkers reported the synthesis of
Results and Discussion
As was mentioned above, instead of RuCl3 ·aq, which reacts
with PiPr3 in boiling methanol to give [RuHCl(CO)-
(PiPr3)2],[7] compound 3 has to be used as starting material
for the preparation of 4 (Scheme 1). On treatment of a sus-
pension of 3 in 2-butanol with 3 equiv. of PiPr3 in the pres-
1
ence of H2 a red solution is formed which, due to the H-
and 31P-NMR spectra, contains the dihydrogen complex 5.
This compound was originally prepared by Chaudret et al.
from [Ru(η4-C8H12)(η6-C8H10)], PiPr3, and CHCl3 under 4
atm of dihydrogen.[8] If the red solution obtained from 3
was brought to dryness in vacuo and the oily residue recrys-
tallized from ether, orange crystals of 4 (but not 5) were
[᭛]
Part 46: H. Werner, P. Bachmann, M. Laubender, O. Gevert,
Eur. J. Inorg. Chem. 1998, 1217Ϫ1224.
Eur. J. Inorg. Chem. 1998, 1827Ϫ1834
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
1434Ϫ1948/98/1111Ϫ1827 $ 17.50ϩ.50/0
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J. Wolf, W. Stüer, C. Grünwald, O. Gevert, M. Laubender, H. Werner
FULL PAPER
Scheme 1
osmium analogue 1.[1a] It is best described as a somewhat
distorted variant of a D4d square antiprism with the two
vacant coordination sites in alternate positions at one
square base of this polyhedron. The other square base is
made up by the two phosphorus atoms and the two hydrido
ligands, the positions of which could be located in a differ-
ence Fourier synthesis. The RuϪP and RuϪCl distances of
4 are almost identical to the corresponding bond lengths in
1, and this is also true for the PϪMϪP, PϪMϪCl, and
ClϪMϪCl bond angles (M ϭ Ru, Os). The distances
isolated in 92% yield. The conversion of 5 to 4 is promoted
by the phosphonium salt 6 which is generated as a byprod-
uct in the reaction of 3, PiPr3, 2-butanol, and H2.
˚
RuϪH1 and RuϪH2 of 1.46(5) and 1.56(5) A are in the
range found for other hydridoruthenium(II) and -ru-
thenium(IV) complexes.[9] We note that recently Gusev,
Berke, Eisenstein, Caulton et al. observed that the mol-
ecules [OsH2X2(PiPr3)2] (X ϭ Cl, Br, I) exist in solution as
two rapidly interconverting isomers, one having C2 sym-
metry (as seen in the crystal) and the other having no sym-
metry.[10] In contrast, the tricyclohexylphosphane derivative
13 which was prepared independently by Chaudret and co-
workers[11] and by us (see below), shows a fluxional process
attributed to the interconversion of two symmetrical iso-
mers.
In order to confirm the proposal that the initial product
in the reaction of 3 with triisopropylphosphane under the
conditions used is indeed the dihydrogen complex 5, a sus-
pension of the oligo- or polymeric cycloocta-1,5-diene com-
pound 3 was treated with PiPr3/H2 in 2-butanol in the pres-
ence of NEt3 as a base. After removal of the solvent and
extraction of the residue with pentane, a red oil was ob-
tained which by comparison of the NMR data with those
published by Chaudret is the dihydrogenruthenium(II) de-
rivative 5.[8] This compound reacts with the phosphonium
salt [HPiPr3]Cl (6) in CH2Cl2 to afford, by evolution of gas
The dichlorodihydridoruthenium(IV) compound 4 does
(H2), quantitatively PiPr3 and the dichlorodihydrido com- not only react with phenylacetylene[5] but also with propar-
plex 4. The latter is an orange solid which is readily soluble gylic alcohols and derivatives thereof. The results are sum-
in CH2Cl2 and CHCl3, but almost insoluble in hydro- marized in Scheme 2. The reaction of 4 with PhCϵCH in
1
carbons. The characteristic feature in the H-NMR spec- CH2Cl2 yields a mixture of two products 7 and 8 of which
trum of 4 is the triplet resonance for the two hydrido li- the first is by far the most dominating species. Compound 7
gands in the high-field region at δ ϭ Ϫ12.30.
is exclusively formed if the initially generated mixture, after
The result of the X-ray crystal structure analysis of 4 is removal of the solvent, is treated again with phenylacety-
shown in Figure 1. The coordination geometry around the lene and heated to 80°C for a short period of time. The
six-coordinate metal center is very similar to that of the isolated yield of 7 is then ca. 70%. The minor component
Figure 1. Molecular structure (ORTEP plot) of 4;[a] the hydrogen atoms besides H1 and H2 are omitted for clarity
[a]
˚
Selected bond lengths [A] and angles [°]: RuϪP1 2.270(1), RuϪP2 2.297(1), RuϪCl1 2.400(1), RuϪCl2 2.401(1), RuϪH1 1.46(5),
RuϪH2 1.56(5); P1ϪRuϪP2 111.69(3), Cl1ϪRuϪCl2 84.29(3), P1ϪRuϪCl1 92.18(3), P1ϪRuϪCl2 139.14(3), P2ϪRuϪCl1 145.07(3),
P2ϪRuϪCl2 92.60(3).
1828
Eur. J. Inorg. Chem. 1998, 1827Ϫ1834

Vinylidene Transition-Metal Complexes, 47
FULL PAPER
of the reaction mixture is the benzylcarbene complex 8 tBuCϵCH, which gives the compounds [RuX2(ϭCϭ
which has already been characterized by X-ray crystal CHtBu)(PPh3)2] (X ϭ Cl, Br), follows a similar route.[16] It
structure analysis.[5] Compound 8 belongs to the class of should be mentioned that the formation of styrene from 4
Grubbs-type carbene complexes [RuCl2(ϭCHR)(PRЈ3)2] and phenylacetylene was confirmed by GC/MS analysis.
that were originally prepared from [RuCl2(PPh3)3] and
The synthesis of the vinylcarbene complexes 9 and 10
cyclopropene or diazoalkane derivatives[12] and are now (Scheme 2) from 4 is a somewhat surprising result. Taking
widely used as highly active catalysts for olefin metathesis earlier work by Selegue,[17] Dixneuf,[18] and by some of
including ROMP and RCM.[13]
us[4b][4c][19] into consideration, we anticipated that on treat-
ment of 4 with propargylic alcohols HCϵCCR2OH, in par-
ticular for R ϭ Ph, allenylidenemetal derivatives [RuCl2(ϭ
CϭCϭCR2)(PiPr3)2] would be formed. However, instead of
these species the related vinylcarbene complexes 9 and 10
were obtained. We found that the reaction of 4 with
HCϵCCPh2OH in CH2Cl2 leads to a mixture of products
among which 9 could be detected as a major component by
1H-NMR spectroscopy. In contrast, by using the corre-
sponding acetate HCϵCCPh2OAc as a carbene source,
compound 9 has been isolated in excellent yield. This (vinyl-
carbene)ruthenium(II) derivative was originally prepared by
Grubbs and coworkers from [RuCl2(PPh3)3] and 1,1-di-
phenylcyclopropene followed by ligand exchange of PPh3
for PiPr3.[12c]
Scheme 2
The formerly unknown complex 10, which was isolated
as a violet solid in 70% yield, resembles in its properties the
diphenyl analogue 9. The 1H-NMR spectrum of 10 displays
in the low-field region two doublets at δ ϭ 19.56 and 8.06
with an HϪH coupling of 11.2 Hz which is typical for an
MϭCHϪCHϭCR2 unit.[12][14] In the 13C-NMR spectrum
of 10 the signal for the carbene-C atom appears at δ ϭ
288.3 and is split into a triplet due to PϪC coupling. Mech-
anistically, the formation of 9 and 10 from 4 is best under-
stood if we assume that in analogy to the course of the
reaction of 4 with phenylacetylene a functionalized hydri-
The vinylideneruthenium(II) compound 7 is a brown, do(vinyl)
species
[RuH(CHϭCHCR2ORЈ)Cl2(PiPr3)2]
only moderately air-sensitive solid that has been charac- (RЈ ϭ H, Ac) is generated as an intermediate which yields
terized by elemental analysis and spectroscopic techniques. the product by elimination of HORЈ.
The 13C-NMR spectrum displays two triplets at δ ϭ 341.1
In a similar way to the dihydridoruthenium(IV) com-
and 109.3, which by comparison[4][14] are assigned to the α- pound 4, the hydridoruthenium(II) derivative 5 reacts with
and β-carbon atoms of the vinylidene ligand. In the 31P- phenylacetylene to give the hydrido(phenylvinylidene) com-
NMR spectrum a singlet resonance appears at δ ϭ 29.0, plex 11 (Scheme 3). Moreover, the parent hydrido(vinylid-
the chemical shift of which is similar to that observed at ene) compound 12 was obtained from 5 and acetylene. Al-
δ
ϭ
27.2 for the PPh3 ligands in [RuCl2(ϭCϭ though a clean reaction between 5 and the terminal alkynes
CHtBu)(PPh3)2].[15] With regard to the mechanism of for- occurs, the isolated yields of 11 and 12 is only moderate
mation of 7, we assume that the starting material 4, con- (ca. 40%) mainly due to the good solubility of the products
taining a metal center with a 16-electron configuration, af- in pentane. Quite recently, Olivan, Eisenstein, and Caulton
fords in the initial step of the reaction a 1:1 adduct with the reported that on treatment of [RuHCl(H2)(PtBu2Me)2] with
alkyne. This seven-coordinate species could react by inser- terminal alkynes RCϵCH the analogous hydrido(vinylid-
tion of the alkyne into one of the RuϪH bonds to generate ene) compounds [RuHCl(ϭCϭCHR)(PtBu2Me)2] (R ϭ Ph,
a hydrido(vinyl) intermediate (also with a 16-electron con- SiMe3) are formed which, according to ab initio DFT calcu-
figuration at the metal center). This compound could then lations, possess a distorted trigonal-bipyramidal geometry
give upon addition of a second molecule of PhCϵCH, fol- with the phosphanes in the apical positions.[20] The osmium
lowed by reductive elimination of styrene, the alkyne com- analogue of 11 was recently prepared by Esteruelas et al.
plex [RuCl2(PhCϵCH)(PiPr3)2]. The conversion of this by a different route, namely from the six-coordinate carby-
species to the isomer 7 possibly occurs by a slippage of the ne(hydrido) complex [OsHCl2(ϵCCH2Ph)(PiPr3)2] by elim-
π-bonded alkyne to an η2-CH-coordinated complex which ination of HCl with NaOMe.[21]
undergoes a 1,2-hydrogen migration to yield the final prod-
The 13C-NMR spectra of both 11 and 12 display in the
uct. Quite recently, Wakatsuki et al. showed by ab initio low-field region the typical signals for the vinylidene α- and
MO calculations that the reaction of [RuX2(PPh3)3] with β-carbon atoms at δ ϭ 329.3 and 109.7 (for 11) and at δ ϭ
Eur. J. Inorg. Chem. 1998, 1827Ϫ1834
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J. Wolf, W. Stüer, C. Grünwald, O. Gevert, M. Laubender, H. Werner
Scheme 4
FULL PAPER
Scheme 3
326.3 and 87.1 (for 12) which are all split into triplets due
1
to PϪC coupling. In the H-NMR spectrum the hydride
resonance also appears as a triplet at δ ϭ Ϫ12.48 (for 11)
and Ϫ15.03 (for 12). In contrast to 7, the methyl groups of
the triisopropylphosphane ligands in 11 and 12 are dia-
stereotopic and thus two sets of signals are observed for the
CH3 protons and carbon nuclei in the NMR spectra. It ylphosphane) complex are quite similar and therefore de-
should be mentioned that in agreement with recent work serve no further comment.
from our laboratory[22][23] compounds 11 and 12 react with
The molecular structure of 15 is shown in Figure 2. The
the phosphonium chloride [HPiPr3]Cl to give the carbene ORTEP plot reveals that the configuration around the
complexes [RuCl2(ϭCHCH2R)(PiPr3)2] (R ϭ Ph, H) in ex- metal center is distorted square-pyramidal with the vinyl-
cellent yield.
idene unit in the apical position. In the basal plane the two
The analogues of the chlorohydrido and dichlorodihy- chloro and the two phosphane ligands are trans disposed.
drido compounds 5 and 4 with two PCy3 instead of two Although according to ab initio calculations this geometry
PiPr3 ligands, 13 and 14, are also accessible from the cyclo- represents the energy minimum on the potential surface,[16]
octa-1,5-diene derivative 3 as the starting material. Like 5, it was found that in contrast to 15 the analogous compound
the corresponding ruthenium(II) complex 13 was first pre- [RuBr2(ϭCϭCHtBu)(PPh3)2] possesses a trigonal-bipyr-
pared by Chaudret and coworkers from the ruthenium(0) amidal structure with the PPh3 groups in the apical posi-
compound [Ru(η4-C8H12)(η6-C8H10)].[8] While this work tions.[16] Therefore it seems that for the preferred configura-
was in progress,[24] Grubbs et al. published an experimental tion of the five-coordinate complexes steric requirements
procedure for 13 that followed our methodology using the play a dominant role. The RuϪC1ϪC2 axis is nearly linear
(cycloocta-1,5-diene)ruthenium(II) derivative 3 as the pre- with an RuϪC1 distance that is slightly shorter than in
[16]
cursor.[25] Regarding the dichlorodihydridoruthenium(IV) [RuBr2(ϭCϭCHtBu)(PPh3)2] [1.77(2) A]
and in the six-
˚
complex 14, very recently Chaudret and coworkers reported coordinate compound [RuCl2(ϭCϭCHPh){κ1(P)-Me2-
a synthesis which is different to that one described in this PCH2CH2OMe}{κ2(P,O)-Me2PCH2CH2OMe}] [1.815(2)
but almost identical to that in [RuCl2(ϭCϭCHPh)-
[RuH2(H2)2(PCy3)2] with aqueous HCl in ether.[11] The {κ1(P)-iPr2PCH2CH2OMe}{κ2(P,O)-iPr2PCH2CH2OMe}]
[26]
˚
work and based on the reaction of the “polyhydride” A]
[4a]
˚
same authors also confirmed by VT NMR measurements [1.749(7) A].
The P1ϪRuϪP2 axis is somewhat bent
that 14 shows a fluxional process in solution which is attri- [169.82(7)°] and this is even more so for the Cl1ϪRuϪCl2
buted to the interconversion between two stereoisomers unit [158.31(7)°]. The C1ϪC2 distance is in the expected
having C2v symmetry.[11] Our observations are in agreement range and this is true also for the RuϪCl and RuϪP bond
with these results.[23]
Compound 14 does not only react with CO to give
lengths.
Finally, a special comment is appropriate concerning the
[RuHCl(CO)2(PCy3)2][11] but also with phenylacetylene in interconversion of the ruthenium(II) and ruthenium(IV)
the molar ratio of 1:10 to yield the vinylidene complex 15 complexes 5 and 4 (see Scheme 5). In the context of the
(Scheme 4). Alternatively, 15 can be prepared upon treat- preparation of 4 from 3 it has already been mentioned that
ment of the carbene derivatives 16 and 17 with PhCϵCH. in this process compound 5 is generated as an intermediate
In both cases the isolated yield is 60Ϫ70%. To the best of which reacts with the byproduct 6, after removal of 2-buta-
our knowledge, there has been only one other compound nol, to give 4. However, the surprising observation is that
of the general composition [RuCl2(ϭCϭCHR)(PCy3)2] the red solution, which is initially formed from 3, PiPr3,
(with R ϭ H) reported in the literature which was obtained and H2 in 2-butanol, is quite stable and can be stored for
from [RuCl2(ϭCHPh)(PCy3)2] and a tenfold excess of al- days without the conversion of the two components 5 and
lene.[12d][12e] The phenylvinylidene complex 15 (which is an 6 to the ruthenium(IV) complex 4.
almost air-stable solid) is only sparingly soluble in common
In order to explain this seeming inconsistency it should
organic solvents at room temperature and thus the 1H-, be emphasized that although 5 and 6 react by elimination
13C-, and 31P-NMR spectra were measured in CDCl3 at of H2 to give 4 and PiPr3, in the presence of a secondary
40°C. The NMR data for 15 and the related bis(triisoprop- alcohol such as 2-butanol, or even better 2-propanol, the
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Eur. J. Inorg. Chem. 1998, 1827Ϫ1834

Vinylidene Transition-Metal Complexes, 47
FULL PAPER
Figure 2. Molecular structure (ORTEP plot) of 15;[a] the hydrogen as a proton source which yields the ruthenium(IV) com-
atoms are omitted for clarity
pound almost quantitatively.
This work was supported by the Deutsche Forschungsgemein-
schaft (SFB 347) and the Fonds der Chemischen Industrie. We are
grateful to the latter in particular for a Kekule´ stipend (to W. S.).
Moreover, we thank Dr. W. Buchner and Mrs. M.-L. Schäfer for
NMR measurements, Mrs. R. Schedl and Mr. C. P. Kneis for per-
forming the elemental analyses and DTA measurements, and Mrs.
I. Geiter for technical assistance. Generous support by the BASF
AG and the Degussa AG (gifts of chemicals) is also gratefully
acknowledged.
Experimental Section
All operations were carried out under argon using Schlenk tech-
niques. The starting materials 3,[27] and 16, 17[22] were prepared as
described in the literature. The alkynes were commercial products
from Aldrich, Strem, and ABCR. Ϫ NMR: Bruker AC 200 and
3
AMX 400 [dvt ϭ doublet of virtual triplets; N ϭ J(PH) ϩ 5J(PH)
or 2J(PC) ϩ 4J(PC), respectively]. Ϫ Melting points determined
by DTA.
1. Preparation of [ RuH2Cl2( PiPr3) 2] (4): A suspension of 220
mg (0.79 mmol for n ϭ 1) of 3 in 20 ml of 2-butanol was treated
[a]
˚
with 463 µl (2.37 mmol) of PiPr3 and heated under hydrogen (1.5
bar) for 6 h at 80°C. Upon cooling the resulting red solution to
room temperature, the solvent was removed in vacuo and 5 ml of
diethyl ether was added to the oily residue. After 2 h, an orange
solid crystallized, which was washed with 5 ml of diethyl ether and
dried in vacuo; yield 359 mg (92%); m. p. 60°C (dec.). Ϫ 1H NMR
(200 MHz, CD2Cl2): δ ϭ 2.30 (m, 6 H, PCHCH3), 1.22 [dd,
J(PH) ϭ 14.9, J(HH) ϭ 7.1 Hz, 36 H, PCHCH3], Ϫ12.30 [t,
J(PH) ϭ 19.0 Hz, 2 H, RuH2]. Ϫ 13C NMR (100.6 MHz, CD2Cl2):
δ ϭ 29.7 (m, PCHCH3), 19.6 (s, PCHCH3). Ϫ 31P NMR (162.0
MHz, CD2Cl2): δ ϭ 103.2 (s). Ϫ C18H44Cl2P2Ru (494.5): calcd. C
43.72, H 8.97, Ru 20.44; found C 43.41, H 8.83, Ru 19.85.
Selected bond lengths [A] and angles [°]: RuϪC1 1.747(7),
RuϪP1 2.429(2), RuϪP2 2.410(2), RuϪCl1 2.342(2), RuϪCl2
2.355(2), C1ϪC2 1.33(1), C2ϪC3 1.45(1); C1ϪRuϪCl1 102.8(2),
C1ϪRuϪCl2 98.9(2), C1ϪRuϪP1 94.6(2), C1ϪRuϪP2 94.9(2),
P1ϪRuϪP2 169.82(7), P1ϪRuϪCl1 88.97(7), P1ϪRuϪCl2
88.42(6),
P2ϪRuϪCl1
85.47(7),
P2ϪRuϪCl2
93.59(7),
Cl1ϪRuϪCl2 158.31(7), RuϪC1ϪC2 178.2(6), C1ϪC2ϪC3
129.4(7).
Scheme 5
2. Preparation of [ RuHCl( H2) ( PiPr3) 2] (5) from 3: A suspen-
sion of 119 mg (0.42 mmol für n ϭ 1) of 3 in 15 ml of 2-butanol was
treated with 200 µl (1.02 mmol) of PiPr3 and 117 µl (0.84 mmol) of
NEt3 and then heated for 6 h under hydrogen (1.5 bar) at 80°C.
Upon cooling to room temperature, the solvent was removed in
vacuo and the orange residue was extracted with 15 ml of pentane.
After the extract was brought to dryness in vacuo, a red oil was
obtained which by comparison of the NMR data was identified as
5.[8] Yield almost quantitative.
3. Reaction of Compound 5 with [ HPiPr3] Cl (6): A solution of
compound 5, prepared from 25 mg (0.09 mmol) of 3, 45 µl (0.23
mmol) of PiPr3 and 25 µl (0.18 mmol) of NEt3 in 5 ml of 2-butanol,
was brought to dryness in vacuo. The oily residue was extracted
with 10 ml of pentane and, after removal of the solvent, was dis-
solved in 3 ml of CH2Cl2. The red solution was treated with 37 mg
(0.19 mmol) of 6, which led to a rapid evolution of gas (H2). After
the solution was stirred for 5 min, the solvent was removed and the
remaining orange solid identified as 4 by comparison of the NMR
data with those of an authentic sample. Yield almost quantitative.
mixture of 4 and triisopropylphosphane is reconverted to 5
and 6. The formation of acetone as a byproduct has been
confirmed by GC/MS analysis which indicates that 2-pro-
panol serves as the hydrogen source. An analogous but sig-
nificantly slower reaction takes place between compound
14 and PCy3 in 2-propanol. In this case the chlorohydrido
complex 13 precipitates due to its lower solubility (com-
pared with 5) in the alcohol. The 31P-NMR spectrum of
the mother liquor indicates that besides 13 a small quantity
of a sideproduct is formed which has not been identified as
yet. For the conversion of 13 to 14 it is preferable to use
4. Preparation of [ RuCl2( ϭCϭCHPh) ( PiPr3) 2] (7): A solution
of 142 mg (0.29 mmol) of 4 in 10 ml of CH2Cl2 was treated with
63 µl (0.57 mmol) of phenylacetylene and stirred for 5 min at room
temperature. The solvent was removed in vacuo to give a red oil
which according to the 1H- and 31P-NMR spectra consisted of a
mixture of 7 (90%) and 8 (10%). The oily material was dissolved
instead of the phosphonium salt [HPCy3]Cl aqueous HCl in 5 ml of benzene, the solution was treated with 30 µl (0.27 mmol)
Eur. J. Inorg. Chem. 1998, 1827Ϫ1834 1831

J. Wolf, W. Stüer, C. Grünwald, O. Gevert, M. Laubender, H. Werner
FULL PAPER
of phenylacetylene and heated for 10 min at 80°C. After cooling
(both s, PCHCH3). Ϫ 31P NMR (162.0 MHz, C6D6): δ ϭ 50.4 (s).
to room temperature, the solvent was removed in vacuo and 3 ml Ϫ C26H49ClP2Ru (560.2): calcd. C 55.75, H 8.82; found C 55.47,
of methanol were added to the brownish residue. Upon storing the
mixture for 2 h, a brown microcrystalline solid was obtained which
was separated from the mother liquor and dried in vacuo; yield 113
H 8.49.
8. Preparation of [ RuHCl( ϭCϭCH2) ( PiPr3) 2] (12): A solution
of compound 5, prepared from 122 mg (0.43 mmol for n ϭ 1) of
3, 215 µl (1.10 mmol) of PiPr3, and 120 µl (0.87 mmol) of NEt3 in
20 ml of 2-propanol under hydrogen, was brought to dryness in
vacuo and the oily residue was extracted with 20 ml of hexane. A
slow stream of acetylene was passed at Ϫ78°C through the hexane
solution, which led to a rapid change of color from red to brown.
The solvent was removed at 0°C in vacuo and the residue was
worked up as described for 11. A brown solid was obtained; yield
85 mg (41%); m. p. 83°C (dec.). Ϫ 1H NMR (400 MHz, C6D6):
δ ϭ 2.64 (m, 8 H, PCHCH3 and ϭCϭCH2), 1.28, 1.24 both m, in
1H{31P} d, J(HH) ϭ 7.2 Hz, 36 H, PCHCH3], Ϫ15.03 [t, J(PH) ϭ
18.3 Hz, 1 H, RuH], signal of ϭCϭCH2 obscured by signal of
PCHCH3. Ϫ 13C NMR (100.6 MHz, C6D6): δ ϭ 326.3 [t, J(PC) ϭ
14.6 Hz, ϭCϭCH2], 87.1 [t, J(PC) ϭ 3.7 Hz, ϭCϭCH2], 24.4 [vt,
N ϭ 19.5 Hz, PCHCH3], 20.4, 20.3 (each s, PCHCH3). Ϫ 31P NMR
(162.0 MHz, C6D6): δ ϭ 51.0 (s). Ϫ C20H45ClP2Ru (484.1): calcd.
C 49.63, H 9.37; found C 49.36, H 9.11.
1
mg (66%); m. p. 97°C (dec.). Ϫ H NMR (400 MHz, C6D6): δ ϭ
7.23Ϫ7.02 (m, 5 H, C6H5), 4.71 [t, J(PH) ϭ 3.6 Hz, 1 H, ϭCϭ
CHPh], 2.79 (m, 6 H, PCHCH3), 1.29 [dvt, N ϭ 13.2, J(HH) ϭ
6.6 Hz, 36 H, PCHCH3]. Ϫ 13C NMR (100.6 MHz, C6D6): δ ϭ
341.1 [t, J(PC) ϭ 15.1 Hz, ϭCϭCHPh], 133.8 [t, J(PC) ϭ 2.5 Hz,
ipso-C of C6H5], 128.5, 125.6, 124.4 (each s, C6H5), 109.3 [t,
J(PC) ϭ 4.3 Hz, ϭCϭCHPh], 23.7 [vt, N ϭ 19.0 Hz, PCHCH3],
20.1 (s, PCHCH3). Ϫ 31P NMR (162.0 MHz, C6D6): δ ϭ 29.0 (s).
Ϫ C26H48Cl2P2Ru (594.6): calcd. C 52.52, H 8.14; found C 52.85,
H 7.86.
5. Preparation of [ RuCl2( ϭCHCHϭCPh2) ( PiPr3) 2] (9) from 4:
A solution of 116 mg (0.23 mmol) of 4 in 10 ml of CH2Cl2 was
treated with 121 mg (0.48 mmol) of HCϵCCPh2OAc and stirred
for 1 h at room temperature. The solvent was removed in vacuo
and 5 ml of pentane was added to the oily residue. After the mix-
ture was stored for 2 h, a red solid precipitated which was filtered
and dried in vacuo. It was identified by comparison of the 1H- and
13C-NMR data with those reported by Grubbs et al. for com-
pound 9.[12b]
9. Preparation of [ RuHCl( H2) ( PCy3) 2] (13) from 3: A suspen-
sion of 220 mg (0.79 mmol for n ϭ 1) of 3 in 20 ml of 2-butanol
was treated with 886 mg (3.16 mmol) of PCy3 and heated for 6 h
under hydrogen (1.5 bar) at 80°C. After the reaction mixture was
cooled to room temperature, the solution was decanted from the
precipitate. The orange solid was washed twice with 10 ml of 2-
butanol and dried in vacuo. It was characterized by comparison of
the 1H- and 31P-NMR data with those found in the literature.[8]
Yield 470 mg (85%).
6. Preparation of [ RuCl2( ϭCHCHϭCiPr2) ( PiPr3) 2] (10): A
solution of 120 mg (0.24 mmol) of 4 in 10 ml of CH2Cl2 was treated
with 85 µl (0.55 mmol) of HCϵCCiPr2OH and stirred for 10 min
at 60°C. After cooling to room temperature, the solvent was re-
moved in vacuo. Upon addition of 5 ml of pentane, a purple solid
precipitated which was filtered and dried in vacuo; yield 103 mg
(70%); m. p. 124°C (dec.). Ϫ 1H NMR (400 MHz, C6D6): δ ϭ 19.56
[d, J(HH) ϭ 11.2 Hz, 1 H, ϭCHCHϭCiPr2], 8.06 [d, J(HH) ϭ
11.2 Hz, 1 H, ϭCHCHϭCiPr2], 3.87 [sept, J(HH) ϭ 6.8 Hz, 1 H,
CHCH3], 2.82 (m, 6 H, PCHCH3), 2.38 [sept, J(HH) ϭ 6.8 Hz, 1
H, CHCH3], 1.24 [dvt, N ϭ 13.2, J(HH) ϭ 6.6 Hz, 36 H,
PCHCH3], 1.04, 0.98 both d, J(HH) ϭ 6.8 Hz, 12 H, CHCH3]. Ϫ
13C NMR (100.6 MHz, C6D6): δ ϭ 288.3 [t, J(PC) ϭ 7.0 Hz,
ϭCHCHϭCiPr2], 152.4 [s, ϭCHCHϭCiPr2], 143.3 [s, ϭCiPr2],
30.8, 29.0 (both s, CHCH3), 22.3 [vt, N ϭ 19.8 Hz, PCHCH3], 21.8,
19.4 (both s, PCHCH3), 18.3 (s, CHCH3). Ϫ 31P NMR (162.0
MHz, C6D6): δ ϭ 45.5 (s). Ϫ C27H58Cl2P2Ru (616.7): calcd. C
52.59, H 9.48; found C 52.13, H 9.13.
10. Preparation of [ RuH2Cl2( PCy3) 2] (14) from 13: A solution
of 130 mg (0.19 mmol) of 13 in 10 ml of CH2Cl2 was treated with
0.5 ml of a 2  aequous solution of HCl and stirred for 3 h at
room temperature. The resulting dark red mixture was cooled to
Ϫ40°C to remove excess HCl and then filtered. The filtrate was
brought to dryness in vacuo and the dark red microcrystalline solid
1
was dried; yield 119 mg (87%); m. p. 74°C (dec.). ϪThe H- and
31P-NMR data were identical to those reported by Chaudret et
al.[11]
Ϫ
13C NMR (100.6 MHz, CD2Cl2): δ ϭ 38.9 [d, J(PC) ϭ
28.6 Hz, ipso-C of C6H11], 29.4 (s, C6H11), 27.4 [d, J(PC) ϭ 11.0
Hz, C6H11], 26.1 (s, C6H11).
11. Preparation of [ RuCl2( ϭCϭCHPh) ( PCy3) 2] (15): a) A
solution of 119 mg (0.162 mmol) of 14 in 5 ml of CH2Cl2 was
7. Preparation of [ RuHCl( ϭCϭCHPh) ( PiPr3) 2] (11): A solu-
tion of compound 5, prepared from 113 mg (0.40 mmol for n ϭ 1) treated with 178 µl (1.62 mmol) of PhCϵCH at Ϫ78°C. After the
of 3, 193 µl (0.99 mmol) of PiPr3, and 115 µl (0.83 mmol) of NEt3
solution was warmed to room temperature, it was stirred for 30
in 20 ml of 2-propanol under hydrogen, was brought to dryness in
min and then concentrated to ca. 2 ml in vacuo. Addition of 10 ml
vacuo and the oily residue was extracted with 20 ml of hexane. The of acetone led to the precipitation of a purple solid, which was
extract was treated with 96 µl (0.88 mmol) of phenylacetylene and
the solution was stirred for 10 min at room temperature. The sol-
vent was then removed at 0°C in vacuo, the residue was dissolved
in 10 ml of pentane, and the solution was filtered through Celite.
The filtrate was concentrated to ca. 4 ml and then stored at Ϫ78°C.
filtered, washed twice with 10 ml of acetone, and dried; yield 91
mg (67%). Ϫ b) A solution of 172 mg (0.21 mmol) of 16 in 10 ml
of benzene was treated with 226 µl (2.10 mmol) of PhCϵCH and
the resulting brown solution heated for 15 h at 45°C. After the
solution was cooled to room temperature, it was worked up as de-
Olive-green crystals precipitated which were separated from the scribed for a); yield 103 mg (60%); m. p. 88°C (dec.). If instead of
mother liquor, washed with 2 ml of pentane (Ϫ20°C) and dried;
yield 83 mg (37%); m. p. 78°C (dec.). Ϫ 1H NMR (400 MHz,
16 the analogous compound 17 was used as starting material, the
yield of the product was about the same. Ϫ H NMR (200 MHz,
1
C6D6): δ ϭ 7.16Ϫ6.87 (m, 5 H, C6H5), 4.36 [t, J(PH) ϭ 3.4 Hz, 1 CDCl3, 40°C): δ ϭ 7.14Ϫ7.07, 6.90Ϫ6.80 both m, 5 H, C6H5),
H, ϭCϭCHPh], 2.51 (m, 6 H, PCHCH3), 1.24, 1.22 both m, in
1H{31P} d, J(HH) ϭ 7.7 Hz, 36 H, PCHCH3], Ϫ12.48 [t, J(PH) ϭ
4.34 [t, J(PH) ϭ 3.1 Hz, 1 H, ϭCϭCHPh], 2.70Ϫ2.54, 2.14Ϫ2.02,
1.68Ϫ1.50 (each m, C6H11). Ϫ 13C NMR (50.3 MHz, CDCl3,
17.2 Hz, 1 H, RuH]. Ϫ 13C NMR (100.6 MHz, C6D6): δ ϭ 329.3 40°C): δ ϭ 342.8 [t, J(PC) ϭ 15 Hz, ϭCϭCHPh], 133.2, 127.9,
[t, J(PC) ϭ 15.1 Hz, ϭCϭCHPh], 133.8 [t, J(PC) ϭ 2.5 Hz, ipso- 125.1, 123.3, (each s, C6H5) 108.6 (br s, ϭCϭCHPh), 33.3 (vt, N ϭ
C of C6H5], 128.5, 123.6, 123.5 (each s, C6H5), 109.7 [t, J(PC) ϭ
22.0 Hz, ipso-C of C6H11), 30.1 (s, C6H11), 27.9 (vt, N ϭ 8.0 Hz,
3.5 Hz, ϭCϭCHPh], 24.7 [vt, N ϭ 19.4 Hz, PCHCH3], 20.4, 20.2 C6H11). Ϫ 31P NMR (81.0 MHz, CDCl3, 40°C): δ ϭ 22.0 (s). Ϫ
1832
Eur. J. Inorg. Chem. 1998, 1827Ϫ1834

Vinylidene Transition-Metal Complexes, 47
FULL PAPER
[7]
[8]
M. A. Esteruelas, H. Werner, J. Organomet. Chem. 1986, 303,
221Ϫ231.
C44H72Cl2P2Ru (834.98): calcd. C 63.29, H 8.69; found C 63.48,
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Organometallics 1994, 13, 3800Ϫ3804.
12. Conversion of Compound 4 to 5 with PiPr3 and 2-Propanol:
In an NMR tube a suspension of 25 mg (0.05 mmol) of 4 in 0.5
ml of 2-propanol was treated with 20 µl (0.10 mmol) of PiPr3. After
2Ϫ3 min, a clear red solution was formed which due to the 1H-
and 31P-NMR spectra contained the two compounds 5 and 6 in
equimolar amounts. Moreover, the presence of acetone was con-
firmed by GC/MS analysis.
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[11]
13. Conversion of Compound 14 to 13 with PCy3 and 2-Propanol:
A solution of 50 mg (0.068 mmol) of 14 in 5 ml of 2-propanol was
treated with 76 mg (0.272 mmol) of PCy3 at room temperature.
Upon stirring for 12 h an orange precipitate was formed, which
was filtered, washed with 2 ml of 2-propanol and dried in vacuo;
yield 29 mg (61%).
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room temperature. Crystal data (from 25 reflections, 4° < Θ < 11°):
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[12d]
115, 9858Ϫ9859. Ϫ
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ϫ 0.10 ϫ 0.10 mm; Enraf-Nonius CAD4 diffractometer, Mo-Kα
˚
˚
[13b]
28, 446Ϫ452. Ϫ
A. S. K. Hashmi, J. Prakt. Chem. 1997,
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M. Schuster, S. Blechert, Angew. Chem. 1997, 109,
˚
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[14] [14a]
(factor 16.4); T ϭ 173(2) K; ω/θ scan, max. 2θ ϭ 48°; 9081 reflec-
tions measured, 6500 independent (Rint. ϭ 0.0533), 4196 with I >
2σ(I). Intensity data were corrected for Lorentz and polarization
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.
The positions of all hydrogen atoms except of H2 were calculated
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Ϫ
[18d]
Soc., Chem. Commun. 1991, 980Ϫ982. Ϫ
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density ϩ0.819/Ϫ0.685 eAϪ3
.
˚
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[24]
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[27]
[28]
[5]
[6]
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M. O. Albers, E. Singleton, J. E. Yates, Inorg. Synth. 1989, 26,
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Crystallographic data (excluding structure factors) for the struc-
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C. Grünwald, O. Gevert, J. Wolf, P. Gonzalez-Herreo, H.
Werner, Organometallics 1996, 15, 1960Ϫ1962.
´
M. Olivan, E. Clot, O. Eisenstein, K. G. Caulton, Organomet-
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Eur. J. Inorg. Chem. 1998, 1827Ϫ1834
1833

J. Wolf, W. Stüer, C. Grünwald, O. Gevert, M. Laubender, H. Werner
FULL PAPER
[29]
bridge Crystallographic Data Centre as supplementary publi-
cation no. CCDC-102563 . Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (Fax: internat. ϩ 44-1223/336-033;
E-mail: deposit@ccdc.cam.ac.uk).
G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467.
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G. M. Sheldrick, A Program for Crystal Structure Refinement,
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[I98271]
1834
Eur. J. Inorg. Chem. 1998, 1827Ϫ1834