A Series of Vinylidene-, Vinyl-, Carbene- and Carbyneruthenium(II) Complexes with [Ru(PCy3)2] and [Ru(PiPr3)2] as Molecular Building Blocks

Article abstract of DOI:10.1002/ejic.200300496

The hydrido(vinylidene) complexes [RuHCl(=C=CHR)(L)₂] (R=H, tBu, Ph; L=PCy₃, PiPr₃) undergo metathesis reactions in the presence of KX (X=I, NCO, OPh, CH₃CO₂, CF₃CO₂) to give the substitution products [RuHX(=C=CHR)(L)₂] (6-15) in good to excellent yields. Treatment of [RuHX(=C=CHR)(L)₂] with HBF₄ in diethyl ether affords the cationic carbyneruthenium(II) derivatives [RuHX(-=CCH₂R)(OEt₂)(L)₂]BF₄ (17, 18, 20, 21) and [RuH(κ²-O₂CCH₃)(-=CCH₂R)(L)₂]BF₄ (19, 22). The reactions of [RuHCl(=C=CHR)(L)₂] with MX [X= BF₄, PF₆, BPh₄, B(Ar_f)₄] in acetonitrile lead to the formation of cationic five- and six-coordinate vinylruthenium(II) compounds 26a-d and 27a-d of which [Ru(CH=CH₂)(CH₃CN)₂(PCy₃)₂]BPh₄ (26c) has been characterized by X-ray crystallography. The starting material [RuHCl(=C=CHPh)(PiPr₃)₂]₂ reacts with CO to give [RuCl(CH=CHPh)(CO)₂(PiPr₃)₂] (28) and with N₂ to produce [RuCl(CH=CHPh)(N₂)(PiPr₃)₂] (29). The molecular structure of 29 has been determined. Protonation of [Ru(CH=CH₂)(CH₃CN)₂(PCy₃)₂]X and [Ru(CH=CHPh)(CH₃CN)₃(PiPr₃)₂]X with HBF₄ and HB(Ar_f)₄ yields the dicationic carbene-ruthenium(II) complexes [Ru(=CHCH₃)(CH₃CN)₂(PCy₃)₂]X₂ (30a,b) and [Ru(=CHCH₂Ph)(CH₃CN)₃(PiPr₃)₂][B(Ar_f)₄]₂ (31), the latter of which eliminates styrene to give [Ru(CH₃CN)₃(PiPr₃)₂][B(Ar_f)₄]₂ (32).

Full text of DOI:10.1002/ejic.200300496

FULL PAPER
A Series of Vinylidene-, Vinyl-, Carbene- and Carbyneruthenium(II) Complexes
with [Ru(PCy3)2] and [Ru(PiPr3)2] as Molecular Building Blocks
Stefan Jung,[a] Kerstin Ilg,[a] Carsten D. Brandt,[a] Justin Wolf,[a] and Helmut Werner*[a]
Dedicated to Professor Michael F. Lappert on the occasion of his 75th birthday
Keywords: Carbene complexes / Carbyne complexes / Ruthenium / Vinyl complexes / Vinylidene complexes
The hydrido(vinylidene) complexes [RuHCl(=C=CHR)(L)2]
X-ray crystallography. The starting material [RuHCl(=C=
(R = H, tBu, Ph; L = PCy3, PiPr3) undergo metathesis reactions
CHPh)(PiPr3)2] reacts with CO to give [RuCl(CH=CHPh)-
in the presence of KX (X = I, NCO, OPh, CH3CO2, CF3CO2) (CO)2(PiPr3)2] (28) and with N2 to produce [RuCl(CH=
to give the substitution products [RuHX(=C=CHR)(L)2] (6−15)
in good to excellent yields. Treatment of [RuHX(=C=
CHR)(L)2] with HBF4 in diethyl ether affords the cationic
CHPh)(N2)(PiPr3)2] (29). The molecular structure of 29 has
been determined. Protonation of [Ru(CH=CH2)-
(CH3CN)2(PCy3)2]X and [Ru(CH=CHPh)(CH3CN)3(PiPr3)2]X
with HBF4 and HB(Arf)4 yields the dicationic carbene-
ruthenium(II) complexes [Ru(=CHCH3)(CH3CN)2(PCy3)2]X2
(30a,b) and [Ru(=CHCH2Ph)(CH3CN)3(PiPr3)2][B(Arf)4]2 (31),
the latter of which eliminates styrene to give
[Ru(CH3CN)3(PiPr3)2][B(Arf)4]2 (32).
carbyneruthenium(ii
)
derivatives [RuHX(ϵCCH2R)(OEt2)-
(L)2]BF4 (17, 18, 20, 21) and [RuH(κ2-O2CCH3)(ϵCCH2R)-
(L)2]BF4 (19, 22). The reactions of [RuHCl(=C=CHR)(L)2] with
MX [X = BF4, PF6, BPh4, B(Arf)4] in acetonitrile lead to the
formation of cationic five- and six-coordinate vinylruth-
enium(II) compounds 26a−d and 27a−d of which [Ru(CH=
CH2)(CH3CN)2(PCy3)2]BPh4 (26c) has been characterized by
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
and [RuHX(ϭCϭCHPh)(PiPr3)2], their conversion into the
corresponding cationic ruthenium carbynes and into neu-
tral as well as cationic vinylruthenium compounds, and also
the formation of dicationic, five-coordinate ruthenium
carbenes. Some preliminary results have already been com-
municated.[3]
In the context of our investigations on the preparation
and reactivity of vinylideneruthenium() complexes,[1] we
recently reported that the reaction of the five-coordinate
hydrido(vinylidene) compound [RuHCl(ϭCϭCH2)(PCy3)2]
with acids HA, containing an anion that does not coordi-
nate to the metal center, in diethyl ether affords the cationic
carbyne(hydrido)
complex
[RuHCl(ϵCCH3)(PCy3)2-
(OEt2)]ϩ instead of the anticipated isomeric carbene deriva-
tive [RuCl(ϭCHCH3)(PCy3)2(OEt2)]ϩ.[2] This cation, as
well as the corresponding cations with coordinated water or
dimethylaniline instead of diethyl ether, turned out to be a
highly efficient catalyst for olefin metathesis, including the
cross-olefin metathesis of cyclopentene with methylacrylate
to afford multiply unsaturated esters CH2(C5H8)nCHCO2Me
(n ϭ 1Ϫ3). The cations [RuHCl(ϵCCH3)(PCy3)2(S)]ϩ,
however, in the absence of excess HA are rather labile and
decompose in solution within 20 min at room temperature.
For this reason, we set out to prepare more stable ru-
thenium carbynes by modifying the coordination sphere
and using different ruthenium vinylidenes as the precursors.
In this paper we report the synthesis of a series of new
hydrido(vinylidene) complexes [RuHX(ϭCϭCHR)(PCy3)2]
Results and Discussion
The hydrido(dihydrogen) complex [RuHCl(H2)(PCy3)2]
(1), which can be prepared from RuCl3·3H2O in high
yield,[2,4] is not only an appropriate starting material for
[RuHCl(ϭCϭCH2)(PCy3)2] (3) and [RuHCl(ϭCϭCHPh)-
(PCy3)2] (4) but also for the tert-butylvinylidene counter-
part 2 [see Equation (1)]. Treatment of a solution of 1 in
CH2Cl2 with two equivalents of tBuCϵCH at Ϫ78 °C leads
to the formation of 2 which, after removal of the solvent,
was isolated as a brown air-sensitive solid in 72% yield. In
contrast to 3 and 4, compound 2 decomposes slowly in
solution even at low temperatures and thus only 1H and 31
P
1
NMR spectroscopic data could be obtained. The H NMR
spectrum displays the signal for the vinylidene proton as a
triplet at δ ϭ 2.87 ppm and the resonance for the hydride,
also as a triplet, at δ ϭ Ϫ13.89 ppm.
[a]
Institut für Anorganische Chemie der Universität Würzburg,
Am Hubland, 97074 Würzburg, Germany
E-mail: helmut.werner@mail.uni-wuerzburg.de
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DOI: 10.1002/ejic.200300496
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469

S. Jung, K. Ilg, C. D. Brandt, J. Wolf, H. Werner
FULL PAPER
7Ϫ10 in good to excellent yields. Apart from the elemental
analyses, the spectroscopic data support the proposed struc-
ture shown in Scheme 1. Since the IR spectra of 7 and 9
display the symmetric ν(NCO) stretch at 1446 cmϪ1, we
assume that the NCO ligand is N-bonded. In case of an O-
coordination, the corresponding absorption is expected to
(1)
While attempts to replace the chloro ligand in 2 by iodide
or isocyanate led to a mixture of products that could not
be separated by fractional crystallization, a clean reaction
appear below 1200 cmϪ1 [6]
.
Both the hydrido(vinylidene) complex 5, containing two
occurs between 2 and excess CH3CO2K that affords the ace- triisopropylphosphane ligands, and the compounds 11Ϫ15
tato derivative 6 in virtually quantitative yield. The charac- obtained by salt metathesis with KX in THF (Scheme 1)
teristic signals for the ϭCH and the RuH protons appear are considerably more stable than their PCy3 counterparts.
1
in the H NMR spectrum at δ ϭ 2.12 and Ϫ12.48 ppm, In solution (C6H6 or CH2Cl2) they do not decompose even
1
1
respectively, and are split into triplets due to H-31P coup- after 24 h. In the H NMR spectra of 11Ϫ15, the vinyl-
ling. The IR spectrum of 6 shows two bands for the asym- idene ϭCH proton resonates at between δ ϭ 4.25 and 4.40
metric and symmetric OCO stretching modes at 1635 and ppm and the RuH proton at between δ ϭ Ϫ9.3 and Ϫ13.6.
1448 cmϪ1, respectively, which, in agreement with literature In the low-field region the 13C NMR spectra of 11Ϫ15 dis-
data,[5] indicate a chelating coordination of the acetate unit. play two triplets, one between δ ϭ 327 and 338 ppm and
The reactions of compounds 3 and 4, being significantly the other between δ ϭ 108 and 110 ppm, which are assigned
more stable than 2, with both KOCN and CH3CO2K in to the α- and β-carbon atoms of the vinylidene ligand. For
THF proceed cleanly and give the substitution products the Ru(NCO) compound 12 and the Ru(κ2-O2CCR3) de-
Scheme 1
Scheme 2
470
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Vinylidene-, Vinyl-, Carbene- and Carbyneruthenium(II) Complexes
FULL PAPER
rivatives 14 and 15 the positions of the ligand vibrations in of six at ruthenium(). The entering olefin can thus not
the IR spectra are quite similar to those of 7 and 9 and 8 bind to the metal center and can also not initiate the con-
and 10, respectively, and thus an N-linkage for the NCOϪ version of the RuH(ϵCCH3) to the active Ru(ϭCHCH3)
anion and a chelating coordination mode for the car- moiety.
boxylate unit can be assumed.
Taking into consideration the fact that hydrido(vinyli-
The ruthenium vinylidenes 4, 5, 7, 8, 14 and 16 are read- dene)ruthenium compounds [RuHCl(ϭCϭCHR)(PRЈ3)2]
ily protonated with a solution of HBF4 in diethyl ether at react with one equivalent of HCl to give the Grubbs-type
low temperatures to give the six-coordinate cationic carbyne carbene complexes [RuCl2(ϭCHCH2R)(PRЈ3)2],[4] we also
complexes 17Ϫ22 in 55Ϫ73% yield. The products were iso- attempted to convert the relatively stable isocyanato deriva-
lated as light yellow, moderately air-sensitive solids by pre- tive 12 into the corresponding metal carbene. However,
cipitation with diethyl ether. While solutions of the acetato while the dichloro compound 23 was exclusively formed
derivatives 19 and 22 (see Scheme 2) are stable for about with two equivalents of HCl, the reaction of 12 with HCl
one hour, the related compounds 17, 18 and 20, 21 decom- in the molar ratio 1:0.9 gave a mixture of four products.
pose more readily, for example in dichloromethane in ca. Apart from the hydrido(vinylidene) complex 5 three car-
30 min even at 0 °C. Conductivity measurements (in nitro- bene derivatives could be detected, which in the 31P NMR
1
methane) confirm the presence of 1:1 electrolytes. The H spectrum give rise to three singlets at δ ϭ 45.2, 47.0 and
1
NMR spectra of 17 and 18 show a singlet for the methyl 48.3 ppm. The H NMR spectrum of the mixture equally
protons of the carbyne ligand at δ ϭ 2.51 (17) and 2.23 shows three resonances for the carbene RuϭCH proton at
ppm (18), while the spectra of 20Ϫ22 display the resonance δ ϭ 19.06, 19.50 and 19.95 ppm, which are split into triplets
1
(also a singlet) for the CH2Ph protons at δ ϭ 3.66Ϫ4.03 due to H-31P coupling. While the signals at δ ϭ 45.2 (31P)
ppm. The hydride signal appears between δ ϭ Ϫ6.41 and and 19.95 ppm (1H) belong to the dichloro compound
Ϫ7.46 ppm and is thus shifted downfield by ca. 3Ϫ6 ppm 23,[1d,1e] the corresponding resonances at δ ϭ 48.3 (31P)
1
compared with the hydrido(vinylidene) precursors. The H and 19.06 ppm (1H) are assigned to the bis(isocyanato)
NMR spectra of 17, 18 and 20, 21 also confirm the coordi- counterpart 25, which was prepared from 23 and excess
nation of one molecule of diethyl ether which is noteworthy KOCN in THF (see Scheme 3). The mixed ligand
insofar as in the five-coordinate carbyneruthenium com- RuCl(NCO) species 24 is thus characterized by the signals
plexes [RuCl2(ϵCCH2R)(PRЈ3)2]ϩ (R ϭ Ph, tBu; RЈ ϭ Cy, at δ ϭ 47.0 (31P) and 19.50 ppm (1H). To explain the forma-
iPr) the position trans to the carbyne ligand is not occupied tion of the unexpected products 23 and 25 in the reaction
by a solvent molecule.[7]
of 12 with HCl, we assume that the acid attacks both the
Similarly to the chloro derivative [RuHCl(ϵCCH3)- CϭC bond of the vinylidene and the metal, leading to an
(PCy3)2(OEt2)]BF4,[2] the cationic carbyne(hydrido) com- NCO/Cl exchange and formation of both 5 and HNCO.
pounds 17 and 18 also catalyze the ring opening metathesis The starting material 12 can therefore react either with HCl
polymerization (ROMP) of cyclooctene. While for 18, the to give 24 or with HNCO to afford 25. Analogously, the
rate, the yield of the polymer and the ratio of the trans- and reaction of 5 (generated from 12 and HCl) furnishes 23
cis-oriented carbon-carbon double bonds of the polymer (with HCl) and 24 (with HNCO). All attempts to separate
are almost identical to the data obtained with the Grubbs the reaction mixture consisting of 5, 23, 24 and 25 by frac-
catalyst [RuCl2(ϭCHPh)(PCy3)2], for 17 the results are less tional crystallization or low-temperature column chroma-
good. Under the same conditions (CH2Cl2, room tempera- tography failed.
ture, ratio cyclooctene to ruthenium complex ϭ 500:1), the
Since the RuϪCl bond of the hydrido(vinylidene) com-
acetato compound 19 is nearly inert in the ROMP of cyclo- plexes is quite labile, we were tempted to replace the chlo-
octene, which is probably due to the coordination number ride not only by other anions but also by a neutral Lewis
Scheme 3
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S. Jung, K. Ilg, C. D. Brandt, J. Wolf, H. Werner
FULL PAPER
base such as acetonitrile. Treatment of a solution of 3 in
CH2Cl2 with MeCN led, indeed, to a quick change of color
from deep red to brown-yellow but afforded, after conven-
tional workup, the cationic vinyl compound [Ru(CHϭ
CH2)(NCMe)2(PCy3)2]Cl instead of a vinylidene complex.
Because this compound, even as a solid, is rather unstable,
the reaction was repeated in the presence of NaBF4 or
KPF6 and gave the more stable complexes 26a and 26b in
about 90% yield (Scheme 4). Salt metathesis with NaBPh4
and NaB(Arf)4 [Arf ϭ 3,5-C6H3(CF3)2] in methanol led to
the formation of 26c and 26d, respectively. Compounds
26aϪd are red-brown or orange-red, only slightly air-sensi-
tive solids, which, in contrast to the analogous chloride, can
be stored under argon at room temperature for weeks with-
out decomposition. The composition of 26aϪd has been
confirmed by elemental analysis and conductivity measure-
ments. Typical spectroscopic features of 26aϪd are the three
resonances for the vinyl protons which, taking 26a as an
example, appear at δ ϭ 7.38, 4.84 and 4.70 ppm. The signal
at lowest field is a doublet of doublets with a large trans-
1H-1H and a smaller cis-1H-1H coupling and is assigned to
the CHϭCH2 proton. The two other signals are doublets
and belong to the methylene protons. The 31P NMR spectra
of 26aϪd display a single resonance confirming that the
two phosphane ligands are stereochemically equivalent.
The result of the X-ray crystal structure analysis of 26c
is shown in Figure 1. The coordination geometry around
the metal center of the cation corresponds to that of a
square pyramid with the two phosphanes and the two
Figure 1. Molecular structure of 26c (hydrogen atoms are omitted
˚
for clarity); selected bond lengths [A] and angles [°]: RuϪP(1)
2.3975(13), RuϪP(2) 2.3979(12), RuϪN(1) 2.008(4), RuϪN(2)
2.006(4), RuϪC(6) 2.001(5), C(6)ϪC(5) 1.340(7), N(1)ϪC(1)
1.160(6), N(2)ϪC(3) 1.142(6); P(1)ϪRuϪP(2) 171.04(4),
N(1)ϪRuϪN(2)
P(2)ϪRuϪC(6)
N(2)ϪRuϪC(6)
RuϪN(2)ϪC(3)
178.05(15),
96.24(12),
89.52(16),
179.0(4),
P(1)ϪRuϪC(6)
N(1)ϪRuϪC(6)
RuϪN(1)ϪC(1)
N(1)ϪC(1)ϪC(2)
92.48(12),
92.35(16),
176.9(4),
178.7(5),
N(2)ϪC(3)ϪC(4) 179.0(5), RuϪC(6)ϪC(5) 129.8(4)
acetonitriles trans-disposed. The atoms C(5) and C(6) of the units. In contrast to the nearly linear N(1)ϪRuϪN(2) axis,
vinyl ligand (which occupies the apical position) lie in the the P(1)ϪRuϪP(2) axis is slightly bent, with the phos-
same plane as the nitrogen and carbon atoms of the MeCN phorus atoms pointing away from the CHϭCH2 moiety.
Scheme 4
472
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Vinylidene-, Vinyl-, Carbene- and Carbyneruthenium(II) Complexes
FULL PAPER
˚
The distance RuϪC(6) of 2.001(5) A is relatively short but in 92% isolated yield. In the IR spectrum of 29, the ν(N2)
similar to that in other ruthenium compounds with a stretching mode appears at 2067 cmϪ1 and thus at a similar
RuϪC(sp2) bond.[8] The RuϪP bond lengths of 2.3975(13) position as for a [Ru(N2)(PiPr3)] complex with a tetraden-
1
and 2.3979(12) A lie in the expected range and are nearly tate N,S,S,N-bonded chelate ligand.[15] The H NMR spec-
˚
identical to those found in five-coordinate carbenerutheni- trum of 29 displays the two signals for the vinyl protons at
um() complexes containing a [Ru(PCy3)2] fragment.[9,10]
δ ϭ 9.50 (RuCH) and 6.37 ppm (ϭCH) while the reson-
The bis(triisopropylphosphane) compound 5 behaves ances for the corresponding carbon atoms appear at δ ϭ
similarly to 3 and reacts with acetonitrile in CH2Cl2 to give 147.5 (RuC) and 130.2 ppm (CϭC), respectively.
27a (Scheme 4). In the presence of KPF6, the hexafluoro-
The formation of 29 from 5 is reversible. If a solution of
phosphate 27b is formed, which, upon salt metathesis, af- 29 in benzene is stored at room temperature for ca. 2 h, the
fords 27c and 27d. The elemental analyses as well as the 1H NMR spectrum reveals the presence of 5 and 29 in the
spectroscopic data of the vinyl complexes 27aϪd confirm ratio of 2:3. After evaporation of the solvent in vacuo, only
that, in contrast to 26aϪd, three acetonitrile ligands are co- the hydrido(vinylidene) complex can be detected. The elim-
ordinated to the metal center. The smaller cone angle of ination of N2, accompanied by an α-shift of the RuCH pro-
PiPr3 (160°) compared to PCy3 (170°)[11] probably favors ton from carbon to the metal, also takes place in the ther-
the increase of the coordination number from five to six mal reaction of 29, which has been studied by differential
1
in the [Ru(PiPr3)2] derivatives. An uncharged six-coordinate thermal analysis (DTA). The H NMR spectrum of the re-
ruthenium compound of composition [RuCl2(NCMe)2- maining product is identical to that of 5. An analogous re-
(PiPr3)2] has recently been prepared by Katayama and versible formation of a vinylmetal compound has also been
Ozawa from [(p-cymene)RuCl2]2 and PiPr3 in toluene/ observed by Bercaw et al. who reacted [(η5-C5Me5)2TaH(ϭ
acetonitrile.[12] Moreover, Caulton et al. have found that the CϭCH2)] with CO to give [(η5-C5Me5)2Ta(CHϭCH2)(CO)]
hydrido(iodo) complex [RuHI(ϭCϭCHSiMe3)(PtBu2Me)2] and regenerated the hydrido(vinylidene) precursor photo-
reacts with excess methyl isocyanide to give the substituted chemically.[16]
vinylruthenium()
derivative
[Ru(CHϭCHSiMe3)-
The proposed structure of the dinitrogen complex 29 has
been confirmed crystallographically (see Figure 2). As in
(CNMe)3(PtBu2Me)2]I.[13]
An intramolecular migration of the hydride to the α-car- the cationic vinyl compound 26c, the coordination ge-
bon atom of the vinylidene ligand also occurs upon treat- ometry around the metal center is square-pyramidal with
ment of compound 5 with carbon monoxide. This reaction the vinyl ligand in the apical position. The bending of the
is accompanied by a quick change of color from olive-green P(1)ϪRuϪP(2) axis [168.74(3)°] is somewhat more pro-
to red and then to pale yellow. The final product is the nounced than in 26c [171.04(4)°], which could be due to a
six-coordinate dicarbonyl complex 28 (Scheme 5), which is slightly stronger steric repulsion between the phenyl and the
probably formed via the corresponding red, monocarbonyl
complex [RuCl{(E)-CHϭCHPh)}(CO)(PiPr3)2]. This mono-
carbonyl compound was previously prepared in our labor-
atory from [RuHCl(CO)(PiPr3)2] and phenylacetylene and
shown to react readily with CO to give 28.[14]
Scheme 5
Figure 2. Molecular structure of 29 (hydrogen atoms are omitted
˚
for clarity); selected bond lengths [A] and angles [°]: RuϪP(1)
2.4021(7), RuϪP(2) 2.4005(7), RuϪN(1) 1.869(5), RuϪCl
2.3959(19), RuϪC(1) 1.973(3), C(1)ϪC(2) 1.296(5), N(1)ϪN(2)
1.088(8); P(1)ϪRuϪP(2) 168.74(3), N(1)ϪRuϪCl 174.13(17),
P(1)ϪRuϪCl 98.15(9), P(2)ϪRuϪCl 93.12(9), N(1)ϪRuϪP(1)
89.42(17), N(1)ϪRuϪP(2) 90.59(17), ClϪRuϪP(1) 89.33(4),
ClϪRuϪP(2) 89.52(4), ClϪRuϪN(1) 90.63(19), ClϪRuϪC(1)
95.23(11), RuϪN(1)ϪN(2) 179.2(7), RuϪC(1)ϪC(2) 135.0(3),
Quite unexpectedly, the hydride shift to afford a RuCHϭ
CHPh unit can also be initiated by N2. Stirring a solution
of 5 in pentane under an atmosphere of dinitrogen leads to
a smooth change of color from olive-green to red-brown
and gives, after low-temperature crystallization and drying
the precipitate in a stream of N2, the insertion product 29 C(1)ϪC(2)ϪC(3) 125.1(3)
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S. Jung, K. Ilg, C. D. Brandt, J. Wolf, H. Werner
FULL PAPER
isopropyl groups. The RuϪN(1)ϪN(2) axis is perfectly lin- zene or pentane, they could not be separated by fractional
1
ear while in the related complex [RuHCl(N2)(PiPr3)2] the crystallization. The H NMR spectrum of the mixture dis-
bond angle RuϪNϪN is 175(2)°.[17] The bond lengths plays a triplet at δ ϭ 17.32 ppm, assigned to the ϭCH pro-
RuϪN(1) and N(1)ϪN(2) are, respectively, 1.869(5) and ton, and a multiplet, which becomes a doublet in off-reson-
˚
1.088(8)
A
and thus quite similar to those in ance, at δ ϭ 4.22 ppm for the CH2Ph protons of the carbene
ligand of 31. In the 31P NMR spectrum, a single resonance
The reactions of the vinyl complexes [Ru(CHϭ for the 31P nuclei of 31 is observed.
[RuHCl(N2)(PiPr3)2].
CHR)(NCMe)n(L)2]X (L ϭ PCy3: n ϭ 2; L ϭ PiPr3: n ϭ
Stirring the solution of 31 and 32 for 2 h at room tem-
3) with strong acids lead to a conversion of the vinyl ligand perature leads to a complete conversion of 31 into the car-
into a coordinated carbene. While the protonation of 26a bene-free complex 32, which was isolated as a green, moder-
or 26c with excess HBF4 in diethyl ether gives a salt-like ately air-stable solid in 90% yield. As a by-product, styrene
1
product with [Ru(ϭCHCH3)(NCMe)2(PCy3)2]2ϩ as the cat- was detected both by H NMR spectroscopy and GC/MS
Ϫ
1
ion and different ratios of, respectively, PF6Ϫ/BF4 and analysis. Since both the H and 13C NMR spectra of 32
BPh4Ϫ/BF4 as the anion, the reaction of 26b with HBF4 show a single set of signals for the protons and carbon
Ϫ
affords the bis(tetrafluoroborate) 30a cleanly in 75% yield atoms of the CH3CN ligands and since the molecule is dia-
(Scheme 6). In a similar way, compound 30b was prepared magnetic, instead of a trigonal-bipyramidal structure a
on treatment of 26d with Brookhart’s acid [H(OEt2)2]- fluxional square-pyramidal geometry is more likely. With
[B(Arf)4].[18] Both 30a and 30b are yellow, moderately air- regard to the mechanism of the conversion of 31 to 32, we
stable solids, the conductivity of which (in nitromethane) assume, in agreement with results recently reported by Car-
corresponds to that of 1:2 electrolytes. Regarding the spec- mona[19] and Gimeno[20] and their co-workers, that the car-
troscopic data, the most typical features are the signal for bene ligand CHCH2Ph rearranges by an intramolecular
the carbene ϭCH proton at δ ϭ 17.70 (30a) and 17.20 ppm 1,2-H shift to styrene. As the bonding of an olefin to a
1
(30b) in the H NMR spectra and the multiplet for the car- twofold positively charged metal center is, in general, con-
bene carbon atom at δ ϭ 335.1 ppm (30b) in the 13C NMR sidered to be weak, styrene is eliminated from the inter-
spectrum. The single resonance for the phosphorus nuclei mediate and the five-coordinate complex 32 is formed.
in the 31P NMR spectra of 30a and 30b suggests that the
The formation of a metal carbene from a metal vinyl pre-
phosphane ligands are stereochemically equivalent and thus cursor is not without precedence. Casey[21] and Helquist[22]
in a trans disposition. Attempts to generate the dication et al. showed already in 1982 that neutral cyclopentadienyl-
[Ru(ϭCHCH3)(NCMe)2(PCy3)2]2ϩ from [RuCl2(ϭCH- iron compounds with FeϪCRϭCH2 as a linkage can be
CH3)(PCy3)2] by substitution of the chloro ligands for converted with HBF4 into the corresponding cationic car-
acetonitrile failed.
bene derivatives. Similar transformations of neutral vinyl to
In contrast to 26d, the related bis(triisopropylphosphane) monocationic carbene complexes by attack of an electro-
compound 27d reacts with an equimolar amount of [H- phile at the β-carbon atom of the vinyl ligand have since
(OEt2)2][B(Arf)4] in CH2Cl2 at 0 °C to give a 1:1 mixture of been carried by various research groups[23] including
the dicationic complexes 31 and 32. Since both compounds ours.[24] However, we note that: (1) as far we know there
are readily soluble in dichloromethane but insoluble in ben- is no report about the preparation of a dicationic metal
Scheme 6
474
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 469Ϫ480

Vinylidene-, Vinyl-, Carbene- and Carbyneruthenium(II) Complexes
FULL PAPER
ν(NCOsym.) ϭ 1446 cmϪ1
.
1H NMR (200 MHz, C6D6): δ ϭ 2.66
carbene from a monocationic vinylmetal precursor by pro-
tonation, and (2) to the best of our knowledge 30a and 30b
are the first dicationic five-coordinate carbeneruthenium
complexes described as yet.
(t, JP,H ϭ 3.7 Hz, 2 H, RuϭCϭCH2), 2.47Ϫ0.81 (m, 66 H, C6H11),
Ϫ18.30 (t, JP,H ϭ 18.3 Hz, 1 H, RuH) ppm. 31P NMR (81.0 MHz,
C6D6): δ ϭ 43.9 (s) ppm. C39H69NOP2Ru (731.0): calcd. C 64.08,
H 9.51, N. 1.92; found C 63.16, H 9.41, N. 2.07.
Preparation of [RuH(κ2-O2CCH3)(؍C؍CH2)(PCy3)2] (8): This
compound was prepared as described for 6, with 3 (74 mg,
0.10 mmol) and potassium acetate (250 mg, 2.55 mmol) as starting
materials. Pale brown solid; yield 70 mg (94%); m.p. 50 °C (de-
comp). IR (KBr): ν(RuH) ϭ 2064, ν(OCOasym.) ϭ 1601, ν(CϭC) ϭ
Experimental Section
All operations were carried out under argon using Schlenk tech-
niques. The starting materials 1,[4,25] 3Ϫ5,1d][1e,25] 16,[4,25] and
23[1d,1e] were prepared as described in the literature. IR spectra
were recorded on a Bruker IFS 25 FT-IR infrared spectrometer,
and NMR spectra were recorded at room temperature on Bruker
AC 200 and AMX 400 instruments, unless otherwise stated. The
molar conductivity ΛM was determined in nitromethane. Melting
points were measured by differential thermal analysis (DTA) with
a Thermoanalyzer Du Pont 9000. Abbreviations used: s, singlet; d,
doublet; t, triplet; q, quadruplet; sept, septet; m, multiplet; vt, vir-
1
1549, ν(OCOsym.) ϭ 1447 cmϪ1. H NMR (200 MHz, C6D6): δ ϭ
2.74 (t, JP,H ϭ 3.3 Hz, 2 H, RuϭCϭCH2), 2.44Ϫ1.07 (m, 66 H,
C6H11), 1.94 (s, 3 H, CH3CO2), Ϫ11.84 (t, JP,H ϭ 19.1 Hz, 1 H,
RuH) ppm. 13C NMR (100.6 MHz, C6D6): δ ϭ 330.0 (t, JP,C
ϭ
15.3 Hz, RuϭCϭCH2), 197.7 (s, CH3CO2), 84.6 (t, JP,C ϭ 3.8 Hz,
RuϭCϭCH2), 33.1 (vt, N ϭ 17.8 Hz, C1 of C6H11), 29.5, 28.9
(both s, C3,5 of C6H11), 27.6, 27.4 (both vt, N ϭ 10.2 Hz, C2,6 of
C6H11), 26.2 (s, C4 of C6H11), 23.8 (s, CH3CO2) ppm. 31P NMR
(162.0 MHz, C6D6): δ ϭ 39.4 (s) ppm. C40H72O2P2Ru (748.0):
calcd. C 64.23, H 9.70, Ru 13.51; found C 63.70, H 9.00, Ru 13.63.
tual triplet; br, broadened signal; N ϭ 3JP,H ϩ 5JP,H or 1JP,C ϩ 3JP,C
.
Preparation of [RuHCl(؍C؍CHtBu)(PCy3)2] (2): A solution of 1
(177 mg, 0.25 mmol) in CH2Cl2 (15 mL) was treated at Ϫ78 °C
with tert-butylacetylene (0.1 mL, 0.82 mmol). After stirring the re-
action mixture for 30 s, the solvent was removed in vacuo. A brown
solid was obtained, which was washed at Ϫ78 °C with pentane
(6 mL) and dried in vacuo; yield 143 mg (72%); m.p. 80 °C (de-
comp). IR (KBr): ν(RuH) ϭ 2106, ν(CϭC) ϭ 1637 cmϪ1. 1H NMR
(200 MHz, C6D6): δ ϭ 2.87 (t, JP,H ϭ 3.7 Hz, 1 H, RuϭCϭCH),
2.61Ϫ1.20 (m, 66 H, C6H11), 1.27 (s, 9 H, CCH3), Ϫ13.89 (t, JP,H ϭ
17.8 Hz, 1 H, RuH) ppm. 31P NMR (81.0 MHz, C6D6): δ ϭ 39.0
(s) ppm. C42H77ClP2Ru (780.5): calcd. C 64.63, H 9.94; found C
63.95, H 9.72.
Preparation of [RuH(NCO)(؍C؍CHPh)(PCy3)2] (9): This com-
pound was prepared as described for 7, with 4 (133 mg, 0.17 mmol)
and KOCN (300 mg, 3.70 mmol) as starting materials. Olive-green
solid; yield 92 mg (67%); m.p. 50 °C (decomp). IR (KBr):
ν(NCOasym.) ϭ 2205, ν(RuH) ϭ 2071, ν(CϭC) ϭ 1615, ν(NCOsym.
)
ϭ 1446 cmϪ1 1H NMR (200 MHz, C6D6): δ ϭ 7.15Ϫ6.76 (m,
.
5 H, C6H5), 4.34 (t, JP,H ϭ 3.9 Hz, 1 H, RuϭCϭCH), 2.37Ϫ1.17
(m, 66 H, C6H11), Ϫ14.42 (t, JP,H ϭ 17.2 Hz, 1 H, RuH) ppm. 31P
NMR (C6D6, 81.0 MHz): δ ϭ 43.1 (s) ppm. C45H73NOP2Ru
(807.1): calcd. C 66.97, H 9.12, N 1.74; found C 66.80, H 8.89,
N 2.07.
Preparation of [RuH(κ2-O2CCH3)(؍C؍CHPh)(PCy3)2] (10): This
compound was prepared as described for 6, with 4 (81 mg,
0.10 mmol) and potassium acetate (230 mg, 2.34 mmol) as starting
materials. Pale brown solid; yield 68 mg (83%); m.p. 42 °C (dec.).
IR (KBr): ν(RuH) ϭ 2099, ν(CϭC) ϭ 1610, ν(OCOasym.) ϭ 1588,
Preparation of [RuH(κ2-O2CCH3)(؍C؍CHtBu)(PCy3)2] (6): A
solution of 2 (97 mg, 0.12 mmol) in THF (8 mL) was treated with
finely divided potassium acetate (280 mg, 2.85 mmol) and stirred
for 20 min at room temperature. The solvent was evaporated in
vacuo and the residue was extracted with benzene (10 mL). The
extract was dried in vacuo, and the remaining off-white solid was
washed twice with pentane (3 mL each) and dried; yield 93 mg
ν(OCOsym.) ϭ 1446 cmϪ1 1H NMR (200 MHz, C6D6): δ ϭ
.
7.29Ϫ6.92 (m, 5 H, C6H5), 4.35 (t, JP,H ϭ 3.3 Hz, 1 H, RuϭCϭ
CH), 2.31Ϫ1.07 (m, 66 H, C6H11), 1.95 (s, 3 H, CH3CO2), Ϫ10.66
(t, JP,H ϭ 19.1 Hz, 1 H, RuH) ppm. 31P NMR (81.0 MHz, C6D6):
δ ϭ 40.1 (s) ppm. C46H76O2P2Ru (824.1): calcd. C 67.04, H 9.29;
found C 66.20, H 9.25.
(96%); m.p. 50 °C (decomp). IR (KBr): ν(RuH)
ϭ 2053,
ν(OCOasym.) ϭ 1635, ν(CϭC) ϭ 1546, ν(OCOsym.) ϭ 1448 cmϪ1
.
1H NMR (400 MHz, CD2Cl2): δ ϭ 2.12 (t, JP,H ϭ 3.3 Hz, 1 H,
RuϭCϭCH), 1.97Ϫ0.87 (m, 66 H, C6H11), 1.43 (s, 3 H, CH3CO2),
0.73 (s, 9 H, CCH3), Ϫ12.48 (t, JP,H ϭ 19.6 Hz, 1 H, RuH) ppm.
13C NMR (100.6 MHz, CD2Cl2): δ ϭ 180.3 (s, CH3CO2), 114.8 (s,
RuϭCϭCH), 33.4 (vt, N ϭ 17.8 Hz, C1 of C6H11), 32.4 (s, CCH3),
30.1 (s, C3 or C5 of C6H11), 29.4 (s, C3 or C5 of C6H11), 28.2, 28.0
(both vt, N ϭ 10.2 Hz, C2,6 of C6H11), 26.9 (s, C4 of C6H11), 24.4
(s, CH3CO2) ppm; the signal of the RuϭC carbon atom could not
be located exactly. 31P NMR (162.0 MHz, CD2Cl2): δ ϭ 38.0 (s)
ppm. C44H80O2P2Ru (804.1): calcd. C 65.72, H 10.03; found C
65.62, H 10.19.
Preparation of [RuHI(؍C؍CHPh)(PiPr3)2] (11): A solution of 5
(73 mg, 0.13 mmol) in THF (7 mL) was treated with an excess of
finely divided KI (250 mg, 1.51 mmol) and stirred for 20 min at
room temperature. The solvent was evaporated in vacuo, the resi-
due was extracted with benzene (8 mL), and the extract was again
dried in vacuo. After the residue was layered with pentane (5 mL)
and the solution stored at Ϫ78 °C, a brown solid formed which
was washed with small quantities of pentane and dried; yield 71 mg
(84%); m.p. 36 °C (decomp). IR (KBr): ν(RuH) ϭ 2075, ν(CϭC) ϭ
1
Preparation of [RuH(NCO)(؍C؍CH2)(PCy3)2] (7): A solution of
3 (80 mg, 0.11 mmol) in THF (8 mL) was treated with an excess of
finely divided KOCN (400 mg, 4.93 mmol) and stirred for 30 min
at room temperature. A gradual change of color from red-brown
to brown occurred. The solvent was evaporated in vacuo, the resi-
1609 cmϪ1. H NMR (200 MHz, C6D6): δ ϭ 7.54Ϫ6.83 (m, 5 H,
C6H5), 4.33 (t, JP,H ϭ 3.3 Hz, 1 H, RuϭCϭCH), 2.56 (m, 6 H,
PCHCH3), 1.21 (m, 36 H, PCHCH3), Ϫ9.32 (t, JP,H ϭ 18.0 Hz, 1
H, RuH) ppm. 13C NMR (50.3 MHz, C6D6): δ ϭ 326.8 (t, JP,C
ϭ
15.3 Hz, RuϭCϭCHPh), 132.8 (s, ipso-C of C6H5), 128.3, 127.8,
due was extracted with benzene (10 mL), and the extract was again 123.9 (all s, C6H5), 109.1 (t, JP,C ϭ 4.4 Hz, RuϭCϭCHPh), 25.7
dried in vacuo. After the oily residue was layered with pentane
(5 mL), a brown solid precipitated which was separated from the
(vt, N ϭ 20.4 Hz, PCHCH3), 20.4, 20.3 (both s, PCHCH3) ppm.
31P NMR (81.0 MHz, C6D6): δ ϭ 51.6 (s) ppm. C26H49IP2Ru
mother liquor and dried; yield 63 mg (78%); m.p. 42 °C (decomp). (651.6): calcd. C 47.93, H 7.58, Ru 15.51; found C 47.75, H 7.30,
IR (KBr): ν(NCOasym.) ϭ 2219, ν(RuH) ϭ 2072, ν(CϭC) ϭ 1612, Ru 15.46.
Eur. J. Inorg. Chem. 2004, 469Ϫ480
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
475

S. Jung, K. Ilg, C. D. Brandt, J. Wolf, H. Werner
FULL PAPER
Preparation of [RuH(NCO)(؍C؍CHPh)(PiPr3)2] (12): This com-
pound was prepared as described for 11, with 5 (78 mg, 0.14 mmol)
108.9 (t, JP,C ϭ 3.8 Hz, RuϭCϭCHPh), 24.5 (vt, N ϭ 20.4 Hz,
PCHCH3), 20.0, 19.5 (both s, PCHCH3) ppm. 19F NMR
and KOCN (250 mg, 3.08 mmol) as starting materials; reaction (376.5 MHz, C6D6): δ ϭ Ϫ75.2 (s) ppm. 31P NMR (162.0 MHz,
time 15 min. Dark green solid; yield 77 mg (97%); m.p. 56 °C (de-
C6D6): δ ϭ 48.2 (s) ppm. C28H49F3O2P2Ru (637.7): calcd. C 52.74,
comp). IR (KBr): ν(NCOasym.) ϭ 2213, ν(RuH) ϭ 2075, ν(CϭC) ϭ H 7.74, Ru 15.85; found C 52.60, H 7.50, Ru 16.80.
1
1610, ν(NCOsym.) ϭ 1464 cmϪ1. H NMR (200 MHz, C6D6): δ ϭ
Preparation of [RuHI(ϵCCH3)(OEt2)(PCy3)2]BF4 (17): A solution
7.20Ϫ6.75 (m, 5 H, C6H5), 4.29 (t, JP,H ϭ 3.3 Hz, 1 H, RuϭCϭ
of 16 (123 mg, 0.15 mmol) in a 1:1 mixture of CH2Cl2 (5 mL) and
CH), 2.29 (m, 6 H, PCHCH3), 1.12 (m, 36 H, PCHCH3), Ϫ13.37
diethyl ether (5 mL) was treated at Ϫ78 °C with a 1.6  solution
(t, JP,H ϭ 17.4 Hz, 1 H, RuH) ppm. 13C NMR (50.3 MHz, C6D6):
of HBF4 in diethyl ether (0.15 mL, 0.24 mmol). After warming the
solution to 0 °C the solvent was evaporated in vacuo and the resi-
due was layered with diethyl ether (5 mL). A light yellow solid pre-
cipitated, which was filtered, washed with pentane (5 mL) and
δ ϭ 333.3 (t, JP,C ϭ 14.9 Hz, RuϭCϭCHPh), 144.0 (s, NCO), 133.8
(s, ipso-C of C6H5), 128.2, 126.3, 123.8 (all s, C6H5), 110.3 (t, JP,C ϭ
3.8 Hz, RuϭCϭCHPh), 24.7 (vt, N ϭ 20.4 Hz, PCHCH3), 20.2,
20.0 (both s, PCHCH3) ppm. 31P NMR (81.0 MHz, C6D6): δ ϭ
dried; yield 86 mg (59%); m.p. 45 °C (decomp). ΛM
52.3 (s) ppm. C27H49NOP2Ru (566.7): calcd. C 57.22, H, 8.71, N,
2.47; found C 57.24, H 8.62, N 2.47.
1
(ΩϪ1cm2molϪ1) ϭ 54. H NMR (200 MHz, CD2Cl2): δ ϭ 3.42 (q,
JH,H ϭ 7.3 Hz, 4 H, OCH2CH3), 2.51 (s, 3 H, RuϵCCH3),
2.37Ϫ1.32 (m, 66 H, C6H11), 1.15 (t, JH,H ϭ 7.3 Hz, 6 H,
OCH2CH3), Ϫ6.87 (t, JP,H ϭ 15.3 Hz, 1 H, RuH) ppm. 31P NMR
(81.0 MHz, CD2Cl2): δ ϭ 55.7 (s) ppm. C42H80BF4IOP2Ru (977.8):
calcd. C 51.59, H 8.25; found C 51.45, H 7.98.
Preparation of [RuH(OPh)(؍C؍CHPh)(PiPr3)2] (13): This com-
pound was prepared as described for 11, with (209 mg,
0.37 mmol) and KOPh (300 mg, 2.27 mmol) as starting materials;
5
reaction time 10 min. Brown solid; yield 80 mg (35%); m.p. 80 °C
(decomp). IR (KBr): ν(RuH) ϭ 2058, ν(CϭC) ϭ 1606 cmϪ1 1H
.
Preparation of [RuH(NCO)(ϵCCH3)(OEt2)(PCy3)2]BF4 (18): This
compound was prepared as described for 17, from 7 (45 mg,
0.06 mmol) and a 1.6  solution of HBF4 in diethyl ether (0.3 mL,
0.48 mmol). Light yellow solid; yield 39 mg (73%); m.p. 69 °C (de-
comp). ΛM (ΩϪ1cm2molϪ1) ϭ 95. IR (KBr): ν(NCOasym.) ϭ 2229,
NMR (400 MHz, C6D6): δ ϭ 7.25Ϫ6.76 (m, 10 H, C6H5 and
OC6H5), 4.40 (t, JP,H ϭ 3.1 Hz, 1 H, RuϭCϭCH), 2.16 (m, in
1H{31P} sept, JH,H ϭ 7.0 Hz, 6 H, PCHCH3), 1.15, 1.13 (both m,
1
in H{31P} both d, JH,H ϭ 7.0 Hz, 18 H each, PCHCH3), Ϫ13.59
(t, JP,H ϭ 18.3 Hz, 1 H, RuH) ppm. 13C NMR (100.6 MHz, C6D6):
δ ϭ 329.6 (t, JP,C ϭ 15.9 Hz, RuϭCϭCHPh), 133.6, 129.4, 128.5,
128.1, 123.3, 123.2, 118.0, 116.3 (all s, C6H5 and OC6H5), 110.4 (t,
JP,C ϭ 3.8 Hz, RuϭCϭCHPh), 24.5 (vt, N ϭ 19.0 Hz, PCHCH3),
20.3, 20.2 (both s, PCHCH3) ppm. 31P NMR (162.0, MHz C6D6):
δ ϭ 50.5 (s) ppm. C32H54OP2Ru (617.8): calcd. C 62.21, H 8.81;
found C 61.91, H 8.33.
ν(RuH) ϭ 1973, ν(NCOsym.) ϭ 1448 cmϪ1 1H NMR (200 MHz,
.
CD2Cl2): δ ϭ 3.42 (q, JH,H ϭ 7.3 Hz, 4 H, OCH2CH3), 2.23 (s, 3 H,
RuϵCCH3), 2.30Ϫ1.31 (m, 66 H, C6H11), 1.15 (t, JH,H ϭ 7.3 Hz, 6
H, OCH2CH3), Ϫ7.46 (t, JP,H ϭ 16.3 Hz, 1 H, RuH) ppm. 31P
NMR (81.0 MHz, CD2Cl2): δ ϭ 46.8 (s) ppm.
Preparation of [RuH(κ2-O2CCH3)(ϵCCH3)(PCy3)2]BF4 (19): A
solution of 8 (81 mg, 0.11 mmol) in toluene (5 mL) was treated at
0 °C with a 1.6  solution of HBF4 in diethyl ether (0.3 mL,
0.48 mmol) and stirred for 15 min at 0 C. The solvent was evapo-
rated in vacuo, the remaining light yellow resisue was washed with
pentane (5 mL) and dried; yield 61 mg (66%); m.p. 60 °C (decomp).
Preparation of [RuH(κ2-O2CCH3)(؍C؍CHPh)(PiPr3)2] (14): This
compound was prepared as described for 11, with 5 (67 mg,
0.12 mmol) and potassium acetate (250 mg, 2.55 mmol) as starting
materials; reaction time 10 min. Orange-red solid; yield 65 mg
(92%); m.p. 62 °C (decomp). IR (KBr): ν(RuH) ϭ 2021, ν(CϭC) ϭ
ΛM (ΩϪ1cm2molϪ1
ν(OCOasym. 1629, ν(OCOsym.
)
ϭ
113. IR (KBr): ν(RuH)
ϭ
2066,
1603, ν(OCOasym.) ϭ 1586, ν(OCOsym.) ϭ 1449 cmϪ1 1H NMR
.
)
ϭ
)
ϭ
1448 cmϪ1
.
1H NMR
(400 MHz, C6D6): δ ϭ 7.25Ϫ6.84 (m, 5 H, C6H5), 4.31 (t, JP,H
ϭ
(200 MHz, CD2Cl2): δ ϭ 2.50Ϫ1.30 (m, 72 H, C6H11, RuϵCCH3
and CH3CO2), Ϫ7.31 (t, JP,H ϭ 17.0 Hz, 1 H, RuH) ppm. 31P
NMR (81.0 MHz, CD2Cl2): δ ϭ 48.7 (s) ppm.
3.5 Hz, 1 H, RuϭCϭCH), 2.39 (m, in 1H{31P} sept, JH,H ϭ 7.0 Hz,
6 H, PCHCH3), 1.82 (s, 3 H, CH3CO2), 1.28, 1.25 (both m, in
1H{31P} both d, JH,H ϭ 7.0 Hz, 18 H each, PCHCH3), Ϫ10.58 (t,
JP,H ϭ 18.7 Hz, 1 H, RuH) ppm. 13C NMR (100.6 MHz, C6D6):
δ ϭ 335.2 (t, JP,C ϭ 15.3 Hz, RuϭCϭCHPh), 181.3 (s, CH3CO2),
134.9 (s, ipso-C of C6H5), 128.3, 123.8, 123.0 (all s, C6H5), 108.6
(t, JP,C ϭ 3.8 Hz, RuϭCϭCHPh), 24.6 (s, CH3CO2), 24.4 (vt, N ϭ
19.0 Hz, PCHCH3), 20.1, 19.5 (both s, PCHCH3) ppm. 31P NMR
(162.0 MHz, C6D6): δ ϭ 49.1 (s) ppm. C28H52O2P2Ru (583.7):
calcd. C 57.61, H 8.98, Ru 17.31; found C 57.99, H 8.73, Ru 17.84.
Preparation of [RuHCl(ϵCCH2Ph)(OEt2)(PCy3)2]BF4 (20): This
compound was prepared as described for 17, from 4 (93 mg,
0.12 mmol) and a 1.6  solution of HBF4 in diethyl ether (0.2 mL,
0.32 mmol). Light yellow solid; yield 75 mg (65%); m.p. 55 °C (de-
1
comp). ΛM (ΩϪ1cm2molϪ1) ϭ 61. H NMR (200 MHz, CD2Cl2):
δ ϭ 7.42Ϫ6.69 (m, 5 H, C6H5), 4.03 (s, 2 H, RuϵCCH2Ph), 3.44
(q, JH,H ϭ 7.3 Hz, 4 H, OCH2CH3), 2.83Ϫ1.26 (m, 66 H, C6H11),
1.15 (t, JH,H ϭ 7.3 Hz, 6 H, OCH2CH3), Ϫ6.41 (br. s, 1 H, RuH)
Preparation of [RuH(κ2-O2CCF3)(؍C؍CHPh)(PiPr3)2] (15): This
compound was prepared as described for 11, with 5 (153 mg,
0.27 mmol) and CF3CO2K (400 mg, 2.63 mmol) as starting materi-
als. The residue was extracted with toluene (9 mL); reaction time
10 min. Red solid; yield 157 mg (91%); m.p. 54 °C (decomp). IR
ppm. 31P NMR (81.0 MHz, CD2Cl2):
δ ϭ 56.0 (s) ppm.
C48H84BClF4OP2Ru (962.5): calcd. C 59.90, H 8.80; found C 58.91,
H 8.50.
Preparation of [RuHCl(ϵCCH2Ph)(OEt2)(PiPr3)2]BF4 (21): A solu-
(KBr): ν(RuH) ϭ 2044, ν(CϭC) ϭ 1628, ν(OCOasym.) ϭ 1588, tion of 5 (56 mg, 0.10 mmol) in a 1:1 mixture of CH2Cl2 (3 mL) and
ν(OCOsym.) ϭ 1444 cmϪ1 1H NMR (400 MHz, C6D6): δ ϭ diethyl ether (3 mL) was treated at Ϫ78 °C with a 1.6  solution
.
7.22Ϫ6.85 (m, 5 H, C6H5), 4.24 (t, JP,H ϭ 3.5 Hz, 1 H, RuϭCϭ of HBF4 in diethyl ether (0.2 mL, 0.32 mmol). After warming the
CH), 2.29 (m, in 1H{31P} sept, JH,H ϭ 7.0 Hz, 6 H, PCHCH3), solution to 0 °C, the solvent was evaporated in vacuo, and the
1
1.19, 1.16 (both m, in H{31P} both d, JH,H ϭ 7.0 Hz, 18 H each,
PCHCH3), Ϫ11.51 (t, JP,H ϭ 18.4 Hz, 1 H, RuH) ppm. 13C NMR
(100.6 MHz, C6D6): δ ϭ 338.1 (t, JP,C ϭ 15.3 Hz, RuϭCϭCHPh),
163.4 (q, JF,C ϭ 36.9 Hz, CF3CO2), 133.4 (s, ipso-C of C6H5), 128.5,
residue was treated with diethyl ether (10 mL). The suspension was
stirred for 15 min at 0 °C which led to the precipitation of a light
yellow solid. This was separated from the mother liquor, washed
with diethyl ether (5 mL) and dried; yield 40 mg (55%); m.p. 60 °C
124.0, 123.7 (all s, C6H5), 115.2 (q, JF,C ϭ 287.3 Hz, CF3CO2), (decomp). ΛM (ΩϪ1cm2molϪ1
) ϭ
61. 1H NMR (200 MHz,
476  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org
Eur. J. Inorg. Chem. 2004, 469Ϫ480

Vinylidene-, Vinyl-, Carbene- and Carbyneruthenium(II) Complexes
CD2Cl2): 7.41Ϫ7.27 (m, H, C6H5), 3.95 (s, H,
FULL PAPER
CH2Cl2 (10 mL each). The combined extracts were dried in vacuo,
δ
ϭ
5
2
RuϵCCH2Ph), 3.43 (q, JH,H ϭ 7.3 Hz, 4 H, OCH2CH3), 2.76 (m, the remaining brown solid was washed twice with pentane (8 mL
6 H, PCHCH3), 1.31 (m, 36 H, PCHCH3), 1.14 (t, JH,H ϭ 7.3 Hz, each) and dried; yield 307 mg (87%); m.p. 55 °C (dec.). ΛM
6 H, OCH2CH3), Ϫ6.73 (br. s, 1 H, RuH) ppm. 31P NMR
(81.0 MHz, CD2Cl2): δ ϭ 63.6 (s) ppm.
(ΩϪ1cm2molϪ1) ϭ 69. IR (KBr): ν(CN) ϭ 2253 cmϪ1 1H NMR
.
(400 MHz, CD2Cl2): δ ϭ 7.38 (dd, JH,H ϭ 15.8, JH,H ϭ 7.9 Hz, 1
H, CHϭCH2), 4.84 (d, JH,H ϭ 7.9 Hz, 1 H, cis-H of CHϭCH2),
4.70 (d, JH,H ϭ 15.8 Hz, 1 H, trans-H of CHϭCH2), 2.49 (s, 6 H,
CH3CN), 2.24Ϫ1.22 (m, 66 H, C6H11) ppm. 13C NMR
(100.6 MHz, CD2Cl2): δ ϭ 150.2 (br. s, RuCH), 125.5 (s, CN),
117.3 (s, CHϭCH2), 34.3 (vt, N ϭ 16.2 Hz, C1 of C6H11), 29.7 (s,
C3,5 of C6H11), 28.1 (vt, N ϭ 10.2 Hz, C2,6 of C6H11), 26.5 (s, C4
of C6H11), 5.0 (s, CH3CN) ppm. 31P NMR (162.0 MHz, CD2Cl2):
δ ϭ 22.4 (s, PCy3), Ϫ144.0 (sept, JF,P ϭ 709.4 Hz, PF6) ppm.
C42H75F6N2P3Ru (916.0): calcd. C 55.07, H 8.25, N 3.06, Ru 11.03;
found C 54.89, H 7.81, N 3.06, Ru 10.76.
Preparation of [RuH(κ2-O2CCH3)(ϵCCH2Ph)(PiPr3)2]BF4 (22): A
solution of 14 (67 mg, 0.11 mmol) in toluene (7 mL) was treated at
0 °C with a 1.6  solution of HBF4 in diethyl ether (0.4 mL,
0.64 mmol) and stirred for 15 min at 0 °C. The solution was
warmed to room temperature and then concentrated to ca. 1 mL
in vacuo. A light yellow solid precipitated, which was separated
from the mother liquor, washed with pentane (5 mL, 0 °C) and
dried; yield 43 mg (55%); m.p. 48 °C (decomp). ΛM
(ΩϪ1cm2molϪ1) ϭ 96. IR (KBr): ν(RuH) ϭ 2072, ν(OCOasym.) ϭ
1587, ν(OCOsym.) ϭ 1465 cmϪ1 1H NMR (200 MHz, CD2Cl2,
.
Preparation of [Ru(CH؍CH2)(NCCH3)2(PCy3)2]BF4 (26b): This
compound was prepared as described for 26a, from 3 (101 mg,
0.14 mmol) and NaBF4 (250 mg, 2.28 mmol) in a 2:1 mixture of
CH2Cl2 and acetonitrile (15 mL). Orange-red solid; yield 109 mg
(91%); m.p. 52 °C (decomp). ΛM (ΩϪ1cm2molϪ1) ϭ 58. IR (KBr):
295 K): δ ϭ 7.40Ϫ7.18 (m, 5 H, C6H5), 3.90 (s, 2 H, RuϵCCH2Ph),
2.34 (s, 3 H, CH3CO2), 2.33 (m, 6 H, PCHCH3), 1.34 (m, 36 H,
PCHCH3), Ϫ6.90 (br. s, 1 H, RuH) ppm. 1H NMR (200 MHz,
CD2Cl2, 263 K): δ ϭ Ϫ6.75 (t, JP,H ϭ 17.4 Hz, 1 H, RuH) ppm.
31P NMR (81.0 MHz, CD2Cl2, 295 K): δ ϭ 59.1 (br. s) ppm. 31P
1
ν(CN) ϭ 2254 cmϪ1. H NMR (400 MHz, CD2Cl2): δ ϭ 7.21 (dd,
NMR (81.0 MHz, CD2Cl2, 263 K):
δ ϭ 59.0 (s) ppm.
JH,H ϭ 15.6, JH,H ϭ 7.7 Hz, 1 H, CHϭCH2), 4.62 (d, JH,H
ϭ
C28H53BF4O2P2Ru (671.5): calcd. C 50.08, H 7.95; found C 49.73,
H 7.75.
7.7 Hz, 1 H, cis-H of CHϭCH2), 4.54 (d, JH,H ϭ 15.6 Hz, 1 H,
trans-H of CHϭCH2), 2.39 (s, 6 H, CH3CN), 2.25Ϫ1.10 (m, 66 H,
C6H11) ppm. 13C NMR (100.6 MHz, CD2Cl2): δ ϭ 148.7 (br. s,
RuCH), 125.6 (s, CN), 117.1 (s, CHϭCH2), 34.2 (vt, N ϭ 16.2 Hz,
C1 of C6H11), 29.7 (s, C3,5 of C6H11), 28.0 (vt, N ϭ 9.5 Hz, C2,6
of C6H11), 26.5 (s, C4 of C6H11), 5.0 (s, CH3CN) ppm. 31P NMR
(162.0 MHz, CD2Cl2): δ ϭ 22.5 (s) ppm. C42H75BF4N2P2Ru
(857.9): calcd. C 58.80, H 8.81, N 3.27; found C 58.55, H 8.54,
N 3.36.
Reaction of 12 with HCl: A solution of 12 (87 mg, 0.16 mmol) in
benzene (10 mL) was treated with a 0.42  solution of HCl in ben-
zene (0.33 mL, 0.14 mmol) and stirred for 10 min at room tempera-
ture. The solvent was evaporated in vacuo and the red-brown resi-
due was dissolved in C6D6 (0.5 mL). The NMR spectra indicated
that besides the starting material 12 (13%) a mixture of four
products was formed, of which
5 (35%) and [RuCl2(ϭ
CHCH2Ph)(PiPr3)2] (23, 14%) were identified by comparison with
authentic samples.[1d,1e] The other two products were assumed to
Preparation of [Ru(CH؍CH2)(NCCH3)2(PCy3)2]BPh4 (26c):
A
solution of 26a (450 mg, 0.49 mmol) in methanol (20 mL) was
treated with NaBPh4 (200 mg, 0.58 mmol) and stirred for 15 min
at room temperature. An orange-red solid precipitated, which was
separated from the mother liquor, washed three times with meth-
anol (10 mL each) and dried in vacuo; yield 416 mg (78%); m.p.
100 °C (decomp). ΛM (ΩϪ1cm2molϪ1) ϭ 63. IR (KBr): ν(CN) ϭ
be
[RuCl(NCO)(ϭCHCH2Ph)(PiPr3)2]
(24,
19%)
and
[Ru(NCO)2(ϭCHCH2Ph)(PiPr3)2] (25, 19%). Characteristic data
for 24: H NMR (200 MHz, C6D6): δ ϭ 19.50 (t, JH,H ϭ 5.1 Hz,
RuϭCH), 4.15 (d, JH,H ϭ 5.1 Hz, CH2Ph).
1
Preparation of [Ru(NCO)2(؍CHCH2Ph)(PiPr3)2] (25): A solution
of 23 (102 mg, 0.17 mmol) in a mixture of THF (10 mL) and
CH2Cl2 (3 mL) was treated with finely divided KOCN (150 mg,
1.85 mmol) and stirred for 24 h at room temperature. After evapor-
ation of the solvent in vacuo, the residue was extracted twice with
benzene (9 mL each). The combined extracts were dried in vacuo,
the remaining violet solid was washed three times with pentane
(5 mL each) and dried; yield 98 mg (94%); m.p. 82 °C (decomp). IR
1
2244 cmϪ1. H NMR (400 MHz, CD2Cl2): δ ϭ 7.33Ϫ6.86 (m, 21
H, CHϭCH2 and BC6H5), 4.70 (d, JH,H ϭ 7.3 Hz, 1 H, cis-H of
CHϭCH2), 4.63 (d, JH,H ϭ 15.2 Hz, 1 H, trans-H of CHϭCH2),
2.33 (s, 6 H, CH3CN), 2.24Ϫ1.24 (m, 66 H, C6H11) ppm. 13C NMR
(100.6 MHz, CD2Cl2): δ ϭ 164.1 (q, JB,C ϭ 49.6 Hz, ipso-C of
BC6H5), 147.2 (br. s, RuCH), 136.0 (s, CH of BC6H5), 125.7 (q,
JB,C ϭ 3.2 Hz, ortho-C of BC6H5), 121.7 (s, BC6H5), 117.2 (s, CHϭ
(KBr): ν(NCOasym.) ϭ 2230, ν(NCOsym.) ϭ 1450 cmϪ1. H NMR
1
CH2), 34.3 (vt, N ϭ 16.5 Hz, C1 of C6H11), 29.8 (s, C3,5 of C6H11),
28.1 (vt, N ϭ 10.2 Hz, C2,6 of C6H11), 26.5 (s, C4 of C6H11), 4.8
(s, CH3CN) ppm; the signal of the CN carbon atom could not be
located exactly. 31P NMR (162.0 MHz, CD2Cl2): δ ϭ 23.0 (s) ppm.
C66H95BN2P2Ru (1090.3): calcd. C 72.71, H 8.78, N 2.57; found C
72.53, H 7.96, N 2.65.
(400 MHz, C6D6): δ ϭ 19.06 (t, JH,H ϭ 5.2 Hz, 1 H, RuϭCH),
7.24Ϫ7.04 (m, 5 H, C6H5), 3.99 (d, JH,H ϭ 5.2 Hz, 2 H, CH2Ph),
2.14 (m; in 1H{31P} sept, JH,H ϭ 7.0 Hz, 6 H, PCHCH3), 0.98
(dvt, N ϭ 14.0, JH,H ϭ 7.0 Hz, 36 H, PCHCH3) ppm. 13C NMR
(100.6 MHz, C6D6): δ ϭ 319.5 (br. s, RuϭCH), 139.9 (s, NCO),
136.6 (s, ipso-C of C6H5), 127.9, 127.3, 125.9 (all s, C6H5), 64.3 (s,
CH2Ph), 22.4 (vt, N ϭ 20.4 Hz, PCHCH3), 18.1 (s, PCHCH3) ppm.
31P NMR (162.0 MHz, C6D6): δ ϭ 48.3 (s) ppm. C28H50N2O2P2Ru
(609.7): calcd. C 55.16, H 8.26, N 4.59; found C 54.69, H 8.24,
N 4.44.
Preparation of [Ru(CH؍CH2)(NCCH3)2(PCy3)2][B(Arf)4] (26d): A
suspension of 26a (54 mg, 0.06 mmol) in diethyl ether (6 mL) was
treated at 0 °C with a solution of Na[B(Arf)4] (55 mg, 0.06 mmol)
in diethyl ether (5 mL). After stirring the reaction mixture for
10 min, a white solid precipitated. The solution was filtered and
the filtrate dried in vacuo. The remaining red-brown solid was
Preparation of [Ru(CH؍CH2)(NCCH3)2(PCy3)2]PF6 (26a): A solu-
tion of 3 (270 mg, 0.39 mmol) in a 1:1 mixture of CH2Cl2 and washed three times with pentane (5 mL each) and dried in vacuo;
acetonitrile (30 mL) was treated with KPF6 (250 mg, 1.36 mmol)
and stirred for 35 min at room temperature. A gradual change of
color from red-brown to light brown occurred. The solvent was
evaporated in vacuo and the residue was extracted twice with
yield 94 mg (96%); m.p. 70 °C (decomp). ΛM (ΩϪ1cm2molϪ1) ϭ
78. H NMR (400 MHz, CD2Cl2): δ ϭ 7.72 [br. s, 8 H, ortho-H of
B(Arf)4], 7.57 [br. s, 4 H, para-H of B(Arf)4], 7.29 (dd, JH,H ϭ 15.3,
1
JH,H ϭ 7.6 Hz, 1 H, CHϭCH2), 4.70 (dt, JH,H ϭ 7.6, JP,H ϭ 2.5 Hz,
Eur. J. Inorg. Chem. 2004, 469Ϫ480
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
477

S. Jung, K. Ilg, C. D. Brandt, J. Wolf, H. Werner
FULL PAPER
1 H, cis-H of CHϭCH2), 4.65 (dt, JH,H ϭ 15.3, JP,H ϭ 2.0 Hz, 1 BC6H5), 125.7 (q, JB,C ϭ 3.1 Hz, ortho-C of BC6H5), 24.1 (vt, N ϭ
H, trans-H of CHϭCH2), 2.51 (s, 6 H, CH3CN), 2.25Ϫ1.13 (m, 66 17.3 Hz, PCHCH3), 19.3 (s, PCHCH3), 4.9, 3.3 (both s, CH3CN)
H, C6H11) ppm. 13C NMR (100.6 MHz, CD2Cl2): δ ϭ 161.8 [q,
ppm. The signals of the CN carbon atoms and of the RuCH carbon
JB,C ϭ 49.9 Hz, ipso-C of B(Arf)4], 147.2 (br. s, RuCH), 134.9 [br. atom are probably covered by the signals of the phenyl carbon
s, ortho-C of B(Arf)4], 129.0 [br. q, JF,C ϭ 31.5 Hz, meta-C of atoms. 31P NMR (162.0 MHz, CD2Cl2): δ ϭ 28.6 (s) ppm.
B(Arf)4], 125.4 (s, CN), 124.7 (q, JF,C ϭ 272.4 Hz, CF3), 117.5 [m,
C56H78BN3P2Ru (967.1): calcd. C 69.55, H 8.13, N 4.35; found C
para-C of B(Arf)4], 117.2 (t, JP,C ϭ 3.4 Hz, CHϭCH2), 34.3 (vt, 68.73, H 8.09, N 4.14.
N ϭ 15.2 Hz, C1 of C6H11), 29.8 (s, C3,5 of C6H11), 28.1 (vt, N ϭ
Preparation of [Ru{(E)-CH؍CHPh}(NCCH3)3(PiPr3)2][B(Arf)4]
(27d): This compound was prepared as described for 26d, from 27b
(73 mg, 0.09 mmol) and solution of Na[B(Arf)4] (77 mg,
9.5 Hz, C2,6 of C6H11), 26.4 (s, C4 of C6H11), 5.0 (s, CH3CN) ppm.
19F NMR (376.5 MHz, CD2Cl2): δ ϭ Ϫ62.7 (s) ppm. 31P NMR
(162.0 MHz, CD2Cl2): δ ϭ 22.9 (s) ppm. C74H87BF24N2P2Ru
(1634.3): calcd. C 54.39, H 5.36, N 1.71; found C 53.82, H 5.12,
N 1.68.
a
0.09 mmol) in diethyl ether (6 mL). Red-brown solid; yield 83 mg
(61%); m.p. 70 °C (decomp). ΛM (ΩϪ1cm2molϪ1) ϭ 54. IR (KBr):
1
ν(CN) ϭ 2263 cmϪ1. H NMR (300 MHz, CD2Cl2): δ ϭ 8.44 (dt,
Preparation of [Ru{(E)-CH؍CHPh}(NCCH3)3(PiPr3)2]Cl (27a): A
solution of 5 (81 mg, 0.14 mmol) in CH2Cl2 (8 mL) was treated
with acetonitrile (3 mL, 0.06 mol) and stirred for 10 min at room
temperature. The solvent was evaporated in vacuo, the remaining
light yellow solid was washed twice with pentane (8 mL each) and
dried; yield 87 mg (91%); m.p. 50 °C (decomp). ΛM
JH,H ϭ 16.6, JP,H ϭ 2.1 Hz, 1 H, CHϭCHPh), 7.73 [br. s, 8 H,
ortho-H of B(Arf)4], 7.58 [br. s, 4 H, para-H of B(Arf)4], 7.21Ϫ6.92
(m, 5 H, C6H5), 6.28 (d, JH,H ϭ 16.6 Hz, 1 H, CHϭCHPh),
2.49Ϫ2.40 (m, 12 H, CH3CN and PCHCH3), 2.23 (s, 3 H,
CH3CN), 1.25 (m, 36 H, PCHCH3) ppm. 13C NMR (75.5 MHz,
CD2Cl2): δ ϭ 161.8 [q, JB,C ϭ 49.8 Hz, ipso-C of B(Arf)4], 140.6
(s, ipso-C of C6H5), 134.9 [br. s, ortho-C of B(Arf)4], 133.3 (m, CHϭ
CHPh), 128.9 [qq, JF,C ϭ 31.5, JF,C ϭ 2.9 Hz, meta-C of B(Arf)4],
(ΩϪ1cm2molϪ1) ϭ 56. IR (KBr): ν(CN) ϭ 2251 cmϪ1 1H NMR
.
(200 MHz, CD3CN): δ ϭ 8.74 (dt, JH,H ϭ 17.2, JP,H ϭ 1.8 Hz, 1
H, CHϭCHPh), 7.15Ϫ6.90 (m, 5 H, C6H5), 6.43 (dt, JH,H ϭ 17.2,
JP,H ϭ 1.8 Hz, 1 H, CHϭCHPh), 2.46 (m, 6 H, PCHCH3), 2.38 (s,
9 H, CH3CN), 1.26 (m, 36 H, PCHCH3) ppm. 13C NMR
(50.3 MHz, CD3CN): δ ϭ 164.2 (br. s, RuCH), 142.6 (s, ipso-C of
C6H5), 133.8 (s, CHϭCHPh), 129.2, 124.3, 123.7 (all s, C6H5),
126.9 (s, CN), 24.8 (vt, N ϭ 17.1 Hz, PCHCH3), 19.7 (s, PCHCH3),
5.3, 5.0 (both s, CH3CN) ppm. The second signal of the CN carbon
atoms is probably covered by the signals of the phenyl carbon
atoms. 31P NMR (81.0 MHz, CD3CN): δ ϭ 28.8 (s) ppm.
C32H58ClN3P2Ru (683.3): calcd. C 56.25, H 8.55, N 6.15; found C
55.89, H 8.05, N 5.56.
128.3, 123.8, 123.5 (all s, C6H5), 125.5 (s, CN), 124.7 (q, JF,C
ϭ
272.6 Hz, CF3), 117.6 [m, para-C of B(Arf)4], 24.1 (vt, N ϭ 17.2 Hz,
PCHCH3), 19.2 (s, PCHCH3), 5.6, 4.1 (both s, CH3CN) ppm. The
second signal of the CN carbon atoms and the signal of the RuCH
carbon atom are probably covered by the signals of the phenyl car-
bon atoms. 19F NMR (282.4 MHz, CD2Cl2): δ ϭ Ϫ63.3 (s) ppm.
31P NMR (CD2Cl2, 81.0 MHz):
δ
ϭ
29.2 (s) ppm.
C64H70BF24N3P2Ru (1511.1): calcd. C 50.87, H 4.67, N 2.78; found
C 50.58, H 4.45, N 2.57.
Generation of [RuCl{(E)-CH؍CHPh}(CO)2(PiPr3)2] (28): In an
NMR tube, a solution of 5 (28 mg, 0.05 mmol) in C6D6 (0.5 mL)
was cooled to Ϫ78 °C. The tube was evacuated in vacuo and then
filled with CO. Upon warming to room temperature, a change of
color from olive-green to red and finally to pale yellow occurred.
Preparation of [Ru{(E)-CH؍CHPh}(NCCH3)3(PiPr3)2]PF6 (27b):
This compound was prepared as described for 26a, from 27a
(85 mg, 0.12 mmol) and KPF6 (150 mg, 0.81 mmol) in a 5:3 mix-
ture of CH2Cl2 and acetonitrile (8 mL). Orange solid; yield 73 mg
(77%); m.p. 36 °C (dec.). Λ (ΩϪ1cm2molϪ1) ϭ 66. IR (KBr):
1
The H and 31P NMR spectra of the solution revealed that com-
pound 28 was formed in quantitative yield. It was identified by
comparison of the NMR spectroscopic data with those of an auth-
entic sample.[14]
1
ν(CN) ϭ 2260 cmϪ1. H NMR (200 MHz, CD2Cl2): δ ϭ 8.56 (d,
JH,H ϭ 16.8 Hz, 1 H, CHϭCHPh), 7.20Ϫ6.89 (m, 5 H, C6H5), 6.34
(d, JH,H ϭ 16.8 Hz, 1 H, CHϭCHPh), 2.46 (m; in 1H{31P} sept,
JH,H ϭ 7.4 Hz, 6 H, PCHCH3), 2.42 (s, 6 H, CH3CN), 2.31 (s, 3
H, CH3CN), 1.27 (dvt, N ϭ 12.3, JH,H ϭ 7.4 Hz, 36 H, PCHCH3)
ppm. 13C NMR (50.3 MHz, CD2Cl2): δ ϭ 159.7 (br. s, RuCH),
141.2 (s, ipso-C of C6H5), 133.3 (s, CHϭCHPh), 128.2, 123.6, 123.1
(all s, C6H5), 125.4, 123.3 (both s, CN), 24.1 (vt, N ϭ 17.1 Hz,
PCHCH3), 19.1 (s, PCHCH3), 5.0, 3.3 (both s, CH3CN) ppm. 31P
NMR (81.0 MHz, CD2Cl2): δ ϭ 28.3 (s, PiPr3), Ϫ144.0 (sept,
JF,P ϭ 709.4 Hz, PF6) ppm. C32H58F6N3P3Ru (792.8): calcd. C
48.48, H 7.37, N 5.30; found C 48.07, H 6.95, N 5.44.
Preparation of [RuCl{(E)-CH؍CHPh}(N2)(PiPr3)2] (29): A solu-
tion of 5 (68 mg, 0.12 mmol) in pentane (8 mL) was stirred under
a nitrogen atmosphere for 2 h at room temperature. A change of
color from olive-green to brown occurred and a red-brown solid
precipitated. After storing the solution for 12 h at Ϫ20 °C, the
mother liquor was separated and the remaining red-brown solid
dried in a stream of N2; yield 65 mg (92%); m.p. 34 °C (decomp).
IR (KBr): ν(N2) ϭ 2067 cmϪ1 1H NMR (400 MHz, C6D6): δ ϭ
.
9.50 (dt, JH,H ϭ 16.6, JP,H ϭ 1.5 Hz, 1 H, CHϭCHPh), 7.39Ϫ6.86
(m, 5 H, C6H5), 6.37 (dt, JH,H ϭ 16.6, JP,H ϭ 1.9 Hz, 1 H, CHϭ
Preparation of [Ru{(E)-CH؍CHPh}(NCCH3)3(PiPr3)2]BPh4 (27c):
This compound was prepared as described for 26c, from 27b
(230 mg, 0.23 mmol) and NaBPh4 (200 mg, 0.58 mmol) in meth-
anol (15 mL). Orange-brown solid; yield 162 mg (73%); m.p. 114
°C (decomp). ΛM (ΩϪ1cm2molϪ1) ϭ 42. IR (KBr): ν(CN) ϭ 2258
cmϪ1. 1H NMR (400 MHz, CD2Cl2): δ ϭ 8.48 (d, JH,H ϭ 16.6 Hz,
1 H, CHϭCHPh), 7.35Ϫ6.88 (m, 25 H, C6H5 and BC6H5), 6.30
(d, JH,H ϭ 16.6 Hz, 1 H, CHϭCHPh), 2.46 (m; in 1H{31P} sept,
JH,H ϭ 7.0 Hz, 6 H, PCHCH3), 2.24 (s, 6 H, CH3CN), 2.08 (s, 3
1
CHPh), 2.62 (m; in H{31P} sept, JH,H ϭ 7.2 Hz, 6 H, PCHCH3),
1
1.17, 1.15 (both m; in H{31P} both d, JH,H ϭ 7.2 Hz, 18 H each,
PCHCH3) ppm. 13C NMR (100.6 MHz, C6D6): δ ϭ 147.5 (t, JP,C ϭ
10.8 Hz, RuCH), 138.0 (s, ipso-C of C6H5), 130.2 (t, JP,C ϭ 3.2 Hz,
CHϭCHPh), 127.9, 123.2, 123.1 (all s, C6H5), 22.5 (vt, N ϭ
17.8 Hz, PCHCH3), 18.8, 18.7 (both s, PCHCH3) ppm. 31P NMR
(162.0 MHz, C6D6): δ ϭ 33.3 (s) ppm. C26H49ClN2P2Ru (588.2):
calcd. C 53.10, H 8.40, N 4.76; found C 53.24, H 8.30, N 3.86.
H, CH3CN), 1.27 (dvt, N ϭ 12.6, JH,H ϭ 7.0 Hz, 36 H, PCHCH3) Preparation of [Ru(؍CHCH3)(NCCH3)2(PCy3)2](BF4)2 (30a): A
ppm. 13C NMR (100.6 MHz, CD2Cl2): δ ϭ 164.1 [q, JB,C
ϭ
solution of 26b (275 mg, 0.32 mmol) in CH2Cl2 (8 mL) was treated
49.5 Hz, ipso-C of BC6H5], 140.7 (s, ipso-C of C6H5), 133.2 (s, with a 1.6  solution of HBF4 in diethyl ether (1.0 mL, 1.60 mmol)
CHϭCHPh), 136.0, 128.3, 123.7, 123.4, 121.8 (all s, C6H5 and at room temperature. A change of color from red to yellow-orange
478
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 469Ϫ480

Vinylidene-, Vinyl-, Carbene- and Carbyneruthenium(II) Complexes
occurred. The solvent was evaporated in vacuo, the remaining yel-
FULL PAPER
C88H75B2F48N3P2Ru (2271.1): calcd. C 46.54, H 3.33, N 1.85;
low solid was washed three times with pentane (5 mL each) and found C 46.65, H 3.35, N 2.31.
dried; yield 225 mg (75%); m.p. 55 °C (decomp).
(ΩϪ1cm2molϪ1) ϭ 99. IR (KBr): ν(CN) ϭ 2275 cmϪ1 1H NMR
Λ
.
X-ray Structure Determination of Compounds 26c and 29: Single
crystals of 26c were grown from CH2Cl2 at Ϫ20 °C and those of
29 from pentane at Ϫ78 °C. Crystal data collection parameters for
these structures are presented in Table 1. The data were collected
on a Stoe IPDS diffractometer (26c) and a Bruker Smart Apex
diffractometer (29) using monochromated Mo-Kα radiation (λ ϭ
(200 MHz CD2Cl2): δ ϭ 17.70 (m, 1 H, ϭCHCH3), 2.96 (br.s, 3
H, ϭCHCH3), 2.79 (s, 6 H, CH3CN), 2.53Ϫ1.31 (m, 66 H, C6H11)
δ ϭ 38.0 (s) ppm.
C42H76B2F8N2P2Ru (945.7): calcd. C 53.34, H 8.10, N. 2.96; found
C 53.01, H 7.73, N 3.42.
ppm. 31P NMR (81.0 MHz, CD2Cl2):
˚
0.71073 A). Intensity data were corrected for Lorentz and polari-
Preparation of [Ru(؍CHCH3)(NCCH3)2(PCy3)2][B(Arf)4]2 (30b): A
solution of 26d (94 mg, 0.06 mmol) in CH2Cl2 (8 mL) was treated
at 0 °C with a solution of [H(OEt2)2][B(Arf)4] (58 mg, 0.06 mmol)
in CH2Cl2 (4 mL). A change of color from red to yellow occurred.
After warming the solution to room temperature, the solvent was
evaporated in vacuo, and the remaining yellow solid was washed
three times with pentane (5 mL each) and dried; yield 130 mg
(87%); m.p. 130 °C (decomp). ΛM (ΩϪ1cm2molϪ1) ϭ 139. 1H NMR
(400 MHz, CD2Cl2): δ ϭ 17.20 (q, JH,H ϭ 5.9 Hz, 1 H, ϭCHCH3),
7.72 [br. s, 16 H, ortho-H of B(Arf)4], 7.57 [br. s, 8 H, para-H of
B(Arf)4], 2.87 (d, JH,H ϭ 5.9 Hz, 3 H, ϭCHCH3), 2.75 (s, 6 H,
CH3CN), 2.17Ϫ1.23 (m, 66 H, C6H11) ppm. 13C NMR
zation effects and an empirical absorption correction was applied
(SADABS2.0). The structures were solved by direct methods
(SHELXS-97).[26] Atomic coordinates and anisotropic thermal par-
ameters of the non-hydrogen atoms were refined by the full-matrix
least-squares method on F2 using SHELXL-97.[27] The asymmetric
unit of 26c includes a molecule of dichloromethane, the chloro
atoms of which are disordered (ratio of occupancy factors Cl1/
Cl2:Cl1Ј/Cl2Ј ϭ 82:18). The hydrogen atoms of the vinyl ligand
were found in a difference-Fourier synthesis and refined without
restraints. The positions of all other hydrogen atoms were calcu-
lated according to the ideal geometry and refined by the riding
method. The chloro and the nitrogen ligands of 29 are disordered
and could be refined anisotropically without restraints (occupancy
factor 80:20).
Ref. code MIKMUO (26c) and CCDC-215082 (29) contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [or from the Cambridge Crystallographic Data
Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax: (in-
ternat.) ϩ44-1223-336-033; E-mail: deposit@ccdc.cam.ac.uk].
(100.6 MHz, [D6]acetone): δ ϭ 335.1 (m, RuϭC), 163.0 [q, JB,C
49.6 Hz, ipso-C of B(Arf)4], 135.9 [br. s, ortho-C of B(Arf)4], 130.4
[br. q, JF,C ϭ 31.8 Hz, meta-C of B(Arf)4], 125.7 (q, JF,C
ϭ
ϭ
272.1 Hz, CF3), 118.8 [m, para-C of B(Arf)4], 48.5 (s, ϭCHCH3),
35.3 (vt, N ϭ 19.1 Hz, C1 of C6H11), 30.8 (s, C3, 5 of C6H11), 28.5
(vt, N ϭ 10.2 Hz, C2, 6 of C6H11), 26.1 (s, C4 of C6H11), 5.7 (s,
CH3CN) ppm. The signal of the CN carbon atom could not be
located exactly. 19F NMR (376.5 MHz, [D6]acetone): δ ϭ Ϫ62.9
(s) ppm. 31P NMR (162.0 MHz, [D6]acetone): δ ϭ 41.0 (s) ppm.
C106H100B2F48N2P2Ru (2498.5): calcd. C 50.96, H 4.03, N 1.12;
found C 50.72, H 3.77, N 1.13.
Table 1. Crystal data for complexes 26c and 29
Generation of [Ru(؍CHCH2Ph)(NCCH3)3(PiPr3)2][B(Arf)4]2 (31):
A solution of 27d (48 mg, 0.03 mmol) in CH2Cl2 (5 mL) was
treated at 0 °C with a solution of [H(OEt2)2][B(Arf)4] (32 mg,
0.03 mmol) in CH2Cl2 (3 mL). A change of color from red to light
green occurred. After stirring the solution for 2 min, it was filtered
26c·CH2Cl2
29
Empirical formula
M
C67H97BCl2N2P2Ru C26H49ClN2P2Ru
1189.35 588.13
0.19 ϫ 0.16 ϫ 0.12 0.40 ϫ 0.24 ϫ 0.12
1
and the filtrate was dried in vacuo. The H and 31P NMR spectra
Crystal size (mm)
Crystal system
Space group
of the light green residue revealed that it consisted of equal
triclinic
monoclinic
P21/c (no. 14)
16.4389(8)
10.9929(5)
17.0126(8)
90
105.4450(10)
90
2963.3(2)
4
1.318
173(2)
0.743
50.00
41784
5210 (0.0291)
amounts of 31 and 32. Data for 31: 1H NMR (400 MHz, CD2Cl2):
¯
P1 (no. 2)
1
δ ϭ 17.32 (t, JH,H ϭ 5.1 Hz, 1 H, ϭCHCH3), 4.42 (m; in H{31P}
˚
a (A)
12.7193(17)
15.482(2)
17.447(2)
88.771(16)
79.913(15)
69.452(15)
3164.3(7)
2
d, JH,H ϭ 5.1 Hz, 2 H, CH2Ph) ppm. 31P NMR (162.0 MHz,
CD2Cl2): δ ϭ 51.5 (s) ppm.
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
Preparation of [Ru(NCCH3)3(PiPr3)2][B(Arf)4]2 (32): A solution of
27d (80 mg, 0.05 mmol) in CH2Cl2 (6 mL) was treated with a solu-
tion of [H(OEt2)2][B(Arf)4] (53 mg, 0.05 mmol) in CH2Cl2 (4 mL)
and stirred for 2 h at room temperature. The solution was filtered,
and the filtrate was dried in vacuo. The remaining green solid was
washed twice with pentane (5 mL each) and dried; yield 102 mg
(90%); m.p. 68 °C (decomp). ΛM (ΩϪ1cm2molϪ1) ϭ 153. IR (KBr):
3
˚
V (A )
Z
Dc (g cmϪ3
)
1.227
Temperature (K)
173(2)
0.423
µ (mmϪ1
)
2Θ(max) (°)
No. reflections measured
No. unique reflections
50.06
25291
10533 (0.0637)
1
ν(CN) ϭ 2288 cmϪ1. H NMR (400 MHz, CD2Cl2): δ ϭ 7.72 [br.
s, 16 H, ortho-H of B(Arf)4], 7.57 [br. s, 8 H, para-H of B(Arf)4],
1
2.48 (m; in H{31P} sept, JH,H ϭ 7.2 Hz, 6 H, PCHCH3), 2.40 (s,
(Rint
)
No. observed reflections
6204
5026
9 H, CH3CN), 1.32, 1.31 (both dvt, N ϭ 13.5, JH,H ϭ 7.2 Hz, 18
H each, PCHCH3) ppm. 13C NMR (100.6 MHz, C6D6): δ ϭ 161.8
[q, JB,C ϭ 49.8 Hz, ipso-C of B(Arf)4], 134.9 [br. s, ortho-C of
B(Arf)4], 128.9 [br. q, JF,C ϭ 31.8 Hz, meta-C of B(Arf)4], 127.5 (s,
CN), 124.7 (q, JF,C ϭ 272.7 Hz, CF3), 117.6 [m, para-C of B(Arf)4],
24.0 (vt, N ϭ 19.1 Hz, PCHCH3), 19.0 (s, PCHCH3), 4.7 (s,
CH3CN) ppm. 19F NMR (376.5 MHz, CD2Cl2): δ ϭ Ϫ62.8 (s)
[I Ͼ 2σ(I)]
Parameters refined
686
331
0.0363
0.0827
15.74
R1
wR2
0.0495
0.1280
Reflection/parameter ratio 15.4
Residual electron density
ϩ1.064/Ϫ0.948
ϩ1.025/Ϫ0.343
Ϫ3
˚
(e·A
)
ppm. 31P NMR (162.0 MHz, CD2Cl2):
δ
ϭ
27.9 (s) ppm.
Eur. J. Inorg. Chem. 2004, 469Ϫ480
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
479

S. Jung, K. Ilg, C. D. Brandt, J. Wolf, H. Werner
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480
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