Convenient routes to vinylideneruthenium dichlorides with basic and bulky tertiary phosphine ligands (PPr3i and PCy3)

Article abstract of DOI:10.1021/om980582h

Two synthetic routes to vinylideneruthenium complexes bearing basic and bulky tertiary phosphine ligands, RuCl₂{=C=C(E)R}L₂ [L = PPr₃ⁱ, E = H, R = Ph (3a), t-Bu (3b), ferrocenyl (3c), p-MeO₂CC₆H₄ (3d), p-MeOC₆H₄ (3e); L = PCy₃, E = H, R = Ph (4a), t-Bu (4b), ferrocenyl (4c); L = PPr₃ⁱ, E = SiMe₃, K = Ph (6), 1.1′-ferrocenediyl (7)], have been developed. Treatment of Ru(methallyl)₂(cod) (1) with PPr₃ⁱ and HCl (each 2 equiv) at -20°C provides [RuCl₂(PPr₃ⁱ)₂]_n, which instantly reacts with phenylacetylene and tert-butylacetylene at room temperature to give 3a,b in isolated yields of 61 and 57%, respectively. On the other hand, heating a toluene solution of [RuCl₂(p-cymene)]₂ (2), phosphine (2 equiv/Ru), and alkyne (1 equiv/Ru) at 80°C leads to the selective formation of the corresponding vinylidene complex. A variety of complexes (3a-e, 4a-c, 6, 7) are prepared from terminal alkynes and (trimethylsilyl)acetylene derivatives in 97-52% isolated yields. Treatment of 2 with PPr₃ⁱ (2 equiv/Ru) and MeCN (10 equiv/Ru) in toluene gives RuCl₂(PPr₃ⁱ)₂(NCMe)₂ (5) in 75% yield, which also serves as the precursor for vinylidene complexes. The X-ray crystal structures of 3a, 4a, and 5 are reported.

Full text of DOI:10.1021/om980582h

5190
Organometallics 1998, 17, 5190-5196
Con ven ien t Rou tes to Vin ylid en er u th en iu m Dich lor id es
w ith Ba sic a n d Bu lk y Ter tia r y P h osp h in e Liga n d s (P P r i
3
a n d P Cy3)
Hiroyuki Katayama and Fumiyuki Ozawa*
Department of Applied Chemistry, Faculty of Engineering, Osaka City University,
Sumiyoshi-ku, Osaka 558-8585, J apan
Received J uly 9, 1998
Two synthetic routes to vinylideneruthenium complexes bearing basic and bulky tertiary
phosphine ligands, RuCl2{dCdC(E)R}L2 [L ) PPri , E ) H, R ) Ph (3a ), t-Bu (3b), ferrocenyl
3
(3c), p-MeO2CC6H4 (3d ), p-MeOC6H4 (3e); L ) PCy3, E ) H, R ) Ph (4a ), t-Bu (4b), ferrocenyl
(4c); L ) PPri , E ) SiMe3, R ) Ph (6), 1,1′-ferrocenediyl (7)], have been developed.
3
Treatment of Ru(methallyl)2(cod) (1) with PPri and HCl (each 2 equiv) at -20 °C provides
3
[RuCl2(PPri ) ] , which instantly reacts with phenylacetylene and tert-butylacetylene at room
3 2 n
temperature to give 3a ,b in isolated yields of 61 and 57%, respectively. On the other hand,
heating a toluene solution of [RuCl2(p-cymene)]2 (2), phosphine (2 equiv/Ru), and alkyne (1
equiv/Ru) at 80 °C leads to the selective formation of the corresponding vinylidene complex.
A variety of complexes (3a -e, 4a -c, 6, 7) are prepared from terminal alkynes and
(trimethylsilyl)acetylene derivatives in 97-52% isolated yields. Treatment of 2 with PPri
3
(2 equiv/Ru) and MeCN (10 equiv/Ru) in toluene gives RuCl2(PPri ) (NCMe)2 (5) in 75% yield,
3 2
which also serves as the precursor for vinylidene complexes. The X-ray crystal structures
of 3a , 4a , and 5 are reported.
In tr od u ction
addition, the vinylidene precursors have an advantage
that they may be readily prepared from conventional
terminal alkynes. However, this system has still suf-
fered from the lack of general synthetic routes to the
vinylidene complexes bearing basic and bulky tertiary
A great deal of attention has been focused on ring-
opening metathesis polymerization (ROMP) of cyclic
olefins catalyzed by well-defined transition metal com-
plexes.1,2 We have recently found that vinylideneru-
phosphine ligands. Thus, while the PPri and PCy3
3
thenium dichlorides bearing PPri or PCy3 ligands,
3
complexes can be synthesized by ligand substitution of
the PPh3 analogues,6 their isolated yields are restricted
to 20-30% due to difficulty in separating the complexes
from PPh3 liberated in the systems.3a
RuCl2{dCdC(H)But}L2 (L ) PPri , PCy3), serve as good
3
catalyst-precursors for ROMP of norbornene deriva-
tives.3,4 Although efficiency of the vinylidene complexes
as the initiator is much lower than that of the well-
known Grubbs’ alkylidene complexes, the polymeriza-
tion rate is rapid enough for practical use and the
resulting polymers have high molecular weights with
polydispersity equivalent to the alkylidene systems.5 In
One of the most convenient methods of synthesizing
vinylidenerutheniums of the form RuCl2{dCdC(H)R}-
L2 so far reported is the treatment of RuCl2Ln complexes
with terminal alkynes, which was first demonstrated
in 1991 by Wakatsuki et al. using RuCl2(PPh3)3.6
Despite intensive studies on transition metal vinylidene
complexes in recent years,7 this method has never been
applied to the other phosphine systems, probably due
to the lack of practical routes to dichlororuthenium
precursors other than RuCl2(PPh3)3. Recently, Werner
(1) For reviews, see: (a) Moore, J . S. In Comprehensive Organome-
tallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.;
Pergamon Press Ltd: Oxford, U.K., 1995; Vol. 12, p 1209. (b) Imamo-
glu, Y. Metathesis Polymerization of Olefins and Polymerization of
Alkynes; Kluwer Academic Publishers: Dordrecht, The Netherlands,
1998; Part I. (c) Breslow, D. S. Prog. Polym. Sci. 1993, 18, 1141-1195.
(d) Schrock, R. R. Acc. Chem. Res. 1990, 23, 158-165.
(2) (a) Lynn, D. M.; Mohr, B.; Grubbs, R. H. J . Am. Chem. Soc. 1998,
120, 1627-1628. (b) Maughon, B. R.; Grubbs, R. H. Macromolecules
1997, 30, 3459-3469. (c) Schwab, P.; Grubbs, R. H.; Ziller, J . W. J .
Am. Chem. Soc. 1996, 118, 100-110. (d) Nguyen, S.-B. T.; Grubbs, R.
H.; Ziller, J . W. J . Am. Chem. Soc. 1993, 115, 9858-9859. (e) Mashima,
K.; Tanaka, Y.; Kaidzu, M.; Nakamura, A. Organometallics 1996, 15,
2431-2433.
et al. employed RuH2Cl2(PPri ) , which is prepared from
3 2
[RuCl2(cod)]n and H2 (1.5 bar) in butanol at 80 °C, as
the starting material for RuCl2{dCdC(H)Ph}(PPri ) .8
3 2
Grubbs et al. reported the synthesis of RuCl2(dCdCH2)-
(6) Wakatsuki, Y.; Koga, N.; Yamazaki, H.; Morokuma, K. J . Am.
Chem. Soc. 1994, 116, 8105-8111.
(3) (a) Katayama, H.; Ozawa, F. Chem. Lett. 1998, 67-68. (b)
Katayama, H.; Yoshida, T.; Ozawa, F. J . Organomet. Chem. 1998, 562,
203-206.
(7) For leading references, see: (a) Slugovc, C.; Mereiter, K.; Schmid,
R.; Kirchner, K. J . Am. Chem. Soc. 1998, 120, 6175-6176. (b) Takagi,
Y.; Matsuzaka, H.; Ishii, Y.; Hidai, M. Organometallics 1997, 16, 4445-
4452. (c) Bourgault, M.; Castillo, A.; Esteruelas, M. A.; On˜ate, E.; Ruiz,
N. Organometallics 1997, 16, 636-645. (d) Werner, H.; Lass, R. W.;
Gevert, O.; Wolf, J. Organometallics 1997, 16, 4077-4088. (e) O’Connor,
J . M.; Hiibner, K.; Merwin, R.; Gantzel, P. K.; Fong, B. S. J . Am. Chem.
Soc. 1997, 119, 9, 3631-3632.
(4) Catalytic activity for ROMP of the vinylideneruthenium RuCl2-
(dCdCH2)(PCy3)2 was reported.2c
(5) In our preliminary work,3a the polydispersity of poly(norbornene)
ranging from 2.6 to 4.1 was found with 10 mM of catalyst-precursors.
The value has been improved to 1.3-1.5 by lowering the concentration
of catalyst-precursors to 2.0 mM: Katayama, H.; Ozawa, F. Unpub-
lished result.
(8) Gru¨nwald, C.; Gevert, O.; Wolf, J .; Gonza´lez-Herrero, P.; Werner,
H. Organometallics 1996, 15, 1960-1962.
10.1021/om980582h CCC: $15.00 © 1998 American Chemical Society
Publication on Web 10/24/1998

Convenient Routes to Vinylideneruthenium Dichlorides
Organometallics, Vol. 17, No. 23, 1998 5191
Sch em e 1
Sch em e 2a
a
Fc ) ferrocenyl.
(PCy3)2 by the reaction of RuCl2{dC(H)Ph}(PCy3)2 with
1,2-propadiene.2c We herein report more simple ways
Sch em e 3
to vinylideneruthenium complexes bearing PPri and
3
PCy3 ligands which utilize common ruthenium com-
plexes, Ru(methallyl)2(cod) (1)9 and [RuCl2(p-cymene)]2
(2),10 as the starting materials.
Resu lts a n d Discu ssion
Syn th esis fr om Ru (m eth a llyl)2(cod ) (1). This
route is based on the synthesis of RuBr2(P*P) (P*P )
chiral bidentate phosphines), reported by Genet and co-
workers.9 Complex 1 was dissolved in a mixture of
CH2Cl2 and acetone and treated successively with PPri
29.5) over 26 h. Complex 3a was isolated in 97% yield
as an analytically pure compound by removal of volatile
materials from the reaction system, followed by washing
3
and dry HCl in MeOH (each 2 equiv) at -20 °C (Scheme
1). The initially colorless solution instantly turned
yellow, and a pale yellow crystalline solid was gradually
precipitated from the solution over 30 min. The 1H,
13C{1H}, and 31P{1H} NMR data and the low solubility
of the precipitate in common organic solvents such
as CH2Cl2 and acetone suggested the formation of
the crude product with MeOH. Similarly, the PPri
3
complexes 3b-e were prepared in isolated yields of 96-
52%. The PCy3 complexes 4a -c were synthesized by
this route and isolated as crystals simply by cooling the
reaction solutions. Attempts to prepare PBut -coordi-
3
[RuCl2(PPri ) ] with an oligomeric structure. Since this
nated vinylidene complexes were unsuccessful.
3 2 n
The reaction of 2 with PPri (2 equiv/Ru) in toluene
complex was thermally unstable in solution as well as
in the solid state, the reactions with alkynes were
conducted without isolation.
3
in the absence of terminal alkynes gave a complex
mixture. In the presence of acetonitrile (10 equiv/Ru),
on the other hand, the same reaction provided RuCl2-
Terminal alkynes (10 equiv/1) were added to the
above reaction mixture. On being stirred at room
temperature, the initially heterogeneous systems gradu-
ally turned to deep purple solutions. 31P{1H} NMR
spectroscopy revealed the formation of vinylidene com-
plexes in 70-80% selectivities. Complexes 3a 11 and 3b
were isolated in 61 and 57% yields by this route.
Syn th esis fr om [Ru Cl2(p-cym en e)]2 (2). The vi-
nylidene complexes 3a -e and 4a -c listed in Scheme 2
were synthesized more readily from 2.10 When a
mixture of 2, PPri3 (2 equiv/Ru), and PhCtCH (1 equiv/
Ru) in toluene was heated at 80 °C, the initially reddish
brown solution gradually darkened. 31P{1H} NMR
spectroscopy revealed the formation of RuCl2(p-cymene)-
(PPri ) (NCMe)2 (5)13 in 75% isolated yield, which was
3 2
found to serve as a good precursor for vinylidene
complexes (Scheme 3). The IR spectrum of 5 exhibited
a strong absorption peak at 2265 cm-1, assignable to
the νCN band. The appearance of only one νCN band is
consistent with the mutually trans arrangement of the
1
MeCN ligands. The H NMR spectrum showed one set
of signals arising from the PPri3 ligands (δ 2.87 (m), 1.41
(doublet of virtual triplets)) and a triplet of the MeCN
5
protons (δ 2.37, J PH ) 1.2 Hz). Furthermore, only a
singlet at δ 21.9 was observed in the 31P{1H} NMR
spectrum. These NMR observations indicate the mutu-
ally trans coordination of the two PPri3 ligands. Hence
the all trans geometry around the ruthenium is evi-
denced.
(PPri ) (δ 41.5)12 at the initial stage, which was succes-
3
sively converted to RuCl2{dCdC(H)Ph}(PPri ) (3a ) (δ
3 2
Figure 1 shows the X-ray structure of 5. The ruthe-
nium atom has typical octahedral geometry. The MeCN
ligands bound to ruthenium are slightly bending to
avoid steric repulsion to one of the i-Pr groups of the
phosphine ligand ( Ru-N-C(1) ) 175.6(2)°, N-C(1)-
C(2) ) 178.2(2)). The N-C(1) and C(1)-C(2) distances
(1.146(3) and 1.456(3) Å) are in the typical range of a
(9) (a) Genet, J . P.; Pinel, C.; Ratovelomanana-Vidal, V.; Mallart,
S.; Pfister, X.; Can˜o de Andrade, M. C.; Laffitte, J . A. Tetrahedron:
Asymmetry 1994, 5, 665-674. (b) Genet, J . P.; Pinel, C.; Ratovelo-
manana-Vidal, V.; Mallart, S.; Pfister, X.; Bischoff, L.; Can˜o de
Andrade, M. C.; Darses, S.; Galopin, C.; Laffitte, J . A. Tetrahedron:
Asymmetry 1994, 5, 675-690. (c) Genet, J . P.; Mallart, S.; Pinel, C.;
J uge´, S. Tetrahedron: Asymmetry 1991, 2, 43-46. Complex 1 is
commercially available from J anssen Chimica.
(10) Bennett, M. A.; Smith, A. K. J . Chem. Soc., Dalton Trans. 1974,
233-241.
(11) Complex 3a was recently prepared by another route.8
(12) Serron, S. A.; Nolan, S. P. Organometallics 1995, 14, 4611-
4616.
(13) A related compound RuCl2(PPh3)2(NCMe)2 was reported: Cole-
Hamilton, D. J .; Wilkinson, G. J . Chem. Soc., Dalton Trans. 1979,
1283-1289.

5192 Organometallics, Vol. 17, No. 23, 1998
Katayama and Ozawa
F igu r e 2. ORTEP diagram of RuCl2{dCdC(H)Ph}(PPri )2
3
(3a ) showing 30% probability thermal ellipsoids. Only one
of the two essentially superposable but crystallographically
independent molecules is shown.
F igu r e 1. ORTEP diagram of RuCl2(PPri )2(NCMe)2 (5)
3
showing 50% probability thermal ellipsoids. Selected bond
distances (Å) and angles (deg): Ru-Cl ) 2.4324(5), Ru-P
) 2.4305(6), Ru-N ) 2.010(2), N-C(1) ) 1.146(3), C(1)-
C(2) ) 1.456(3), Cl-Ru-Cl* ) 180.00, P-Ru-P* ) 180.00,
N-Ru-N* ) 180.00, Cl-Ru-P ) 89.96(2), Cl-Ru-N )
87.56(5), P-Ru-N ) 88.24(5), Ru-N-C(1) ) 175.6(2),
N-C(1)-C(2) ) 178.2(2).
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) a n d Dih ed r a l An gles betw een Lea st-Squ a r es
P la n es (d eg) for 3a a n d 4a
3a
4a
Ru-C(1)
Ru-Cl(1)
Ru-Cl(2)
Ru-P(1)
Ru-P(2)
C(1)-C(2)
1.750(4)
2.338(1)
2.3541(9)
2.421(1)
2.424(1)
1.329(5)
1.761(2)
2.3668(7)
2.3623(7)
2.4241(6)
2.4080(6)
1.334(3)
Ru-C(1)-C(2)
Cl(1)-Ru-Cl(2)
P(1)-Ru-P(2)
177.1(3)
158.63(4)
169.17(3)
178.5(2)
156.93(2)
170.94(2)
(Ru, Cl(1), Cl(2), C(1)) vs (C(1),
C(2), C(3))
1.40
6.99
F igu r e 3. ORTEP diagram of RuCl2{dCdC(H)Ph}(PCy3)2‚
CH2Cl2 (4a ) showing 50% probability thermal ellipsoids.
The solvent molecule is omitted for clarity.
nitrogen-carbon triple bond and of a carbon-carbon
single bond, respectively.
The reaction of 5 with phenylacetylene (1 equiv) in
CH2Cl2 was complete within 20 h at 40 °C to give the
vinylidene complex 3a in quantitative yield (NMR).
Complexes 3b,c were similarly prepared using tert-
butylacetylene and ferrocenylacetylene, respectively.
Ch a r a cter iza tion of Vin ylid en e Com p lexes. Vi-
nylidene complexes thus prepared were characterized
by elemental analysis and 1H, 13C{1H}, and 31P{1H}
NMR spectroscopy. The data for 3a were in fair
agreement with those reported.8 The other vinylidene
complexes exhibited 13C{1H} NMR signals characteristic
of the R- and â-vinylidene carbons (δ 337.1-344.6 and
103.2-115.5, respectively).
The structures of vinylidene complexes 3a and 4a
were determined by single-crystal X-ray diffraction
studies. The selected bond distances and angles are
listed in Table 1. As seen from the ORTEP drawings
in Figures 2 and 3, both complexes have a distorted
square pyramidal structure having the vinylidene ligand
at the apical position. The Ru-C(1)-C(2) angles are
almost linear (177.1(3) for 3a ; 178.5(2)° for 4a ), and the
Cl(1)-Ru-Cl(2) and P(1)-Ru-P(2) axes are bent away
from the vinylidene ligand (158.63(4) and 156.93(2)° for
3a ; 169.17(3) and 170.94(2)° for 4a ). The Ru-C(1)
distances (1.750(4) for 3a ; 1.761(2) Å for 4a ) are
comparable to each other and to that of RuBr2{dCd
C(H)But}(PPh3)2 (1.768(17) Å)6 but shorter than those
of the coordinatively saturated vinylideneruthenium
complexes [CpRu{dCdC(Me)Ph}(PPh3)2]+I- (1.863(10)
Å),14
[RuCl{dCdC(H)Ph}(κ2(P,O)-Pri PCH2CH2-
2
OMe)2]+OTf- (1.790(3) Å),15 and TpRuCl{dCdC(H)Ph}-
(PPh3) (1.801(4) Å),16 probably reflecting the apical
arrangement of the vinylidene ligands without trans
(14) Bruce, M. I.; Humphrey, M. G.; Snow, M. R.; Tiekink, E. R. T.
J . Organomet. Chem. 1986, 314, 213-225.
(15) Mart´ın, M.; Gevert, O.; Werner, H. J . Chem. Soc., Dalton Trans.
1996, 2275-2283.

Convenient Routes to Vinylideneruthenium Dichlorides
Organometallics, Vol. 17, No. 23, 1998 5193
Sch em e 4
Sch em e 5a
a
Fc ) ferrocenyl.
lylvinylidene complex but the desilation product 3c in
67% selectivity (NMR). The reaction with Me3SiCtCH
gave a complex mixture of ruthenium species, from
which RuMeCl(CO)(PPri ) (8) was isolated in 15% yield.
3 2
Complex 8 exhibited a strong νCO band at 1893 cm-1 in
the IR spectrum. In the 13C{1H} NMR spectrum,
signals assignable to the carbonyl and methyl carbons
were observed at δ 202.0 (t, 2J PC ) 14 Hz) and -13.4 (t,
2J PC ) 7 Hz), respectively.
donor ligand. The vinylidene groups lie approximately
on the least-squares plane composed of the Ru, Cl(1),
Cl(2), and C(1) atoms. A similar structural feature has
been observed for the alkylidene complex RuCl2{dCH-
(C6H4Cl-p)}(PCy3)2.2c
In both reactions in Scheme 5, the formation of
Me3SiOH was observed by GC-MS spectrometry. Since
the parent silylacetylenes are stable to desilation under
the reaction conditions and desilation was observed only
in the reactions in Scheme 5 (i.e., not in the reactions
in Scheme 4), â-silylvinylidene complexes generated
Syn th esis of â-Silylvin ylid en e Com p lexes. The
present routes could be applied to the synthesis of
â-silylvinylidene complexes via 1,2-silyl migration of
silylacetylenes (Scheme 4).17 The reaction of 2, PCy3
(2 equiv/Ru), and PhCtCSiMe3 (10 equiv/Ru) in toluene
at 60 °C for 51 h gave RuCl2{dCdC(SiMe3)Ph}(PCy3)2
(6). The 13C{1H} NMR spectrum exhibited character-
istic signals assignable to the R- and â-vinylidene
from [RuCl2(PPri ) ] and silylacetylenes are considered
3 2 n
to undergo desilation with the aid of residual water and
HCl in the systems. Actually, isolated 6 was found to
be readily converted into the desilation product 4a at
room temperature in CH2Cl2 in the presence of a small
amount of dilute hydrochloric acid. The formation of
methyl carbonyl complex 8 may be rationalized as
follows. Nucleophilic attack of water on the R-vi-
nylidene carbon of the nonsubstituted vinylidene com-
plex 9, probably with the aid of HCl catalyst, followed
by enol to keto tautomerization of the resulting hy-
droxycarbene complex leads to a 14-electron acetylru-
thenium species, which subsequently undergoes decar-
bonylation to give 8. This type of transformation has
already been documented.18
2
carbons at δ 330.1 (t, J PC ) 12 Hz) and 108.2 (br s),
respectively. The methyl protons and carbons of the
SiMe3 group were observed at δ 0.29 (s) and 1.88 (s) in
1
the H and 13C{1H} NMR spectra, respectively.
When 1,1′-bis{(trimethylsilyl)ethynyl}ferrocene (1
equiv/2) was employed as the starting silylacetylene, a
ferrocene derivative with two (â-silylvinylidene)ruthe-
nium units (7) was obtained in 92% yield. The composi-
tion was confirmed by elemental analysis. The C2-
symmetrical structure was suggested by NMR spec-
troscopy, where a set of signals similar to RuCl2-
{dCdC(H)Fc}(PPri ) (3c, Fc ) ferrocenyl) was observed.
3
Synthesis of â-silylvinylidene complexes was also
examined with 1 as the starting material (Scheme 5).
Exp er im en ta l Section
Gen er a l P r oced u r e a n d Ma ter ia ls. All manipulations
were performed under an argon atmosphere using conven-
tional Schlenk techniques or in a nitrogen-filled glovebox.
Argon gas was purified by passage through P2O5 (Merck,
SICAPENT). 1H, 13C, and 31P NMR spectra were recorded on
a J EOL J NM-A400 or a Varian Mercury 300 spectrometer.
Treatment of [RuCl2(PPri ) ] , in situ generated from
3 2 n
1, with FcCtCSiMe3 did not afford the expected â-si-
(16) Slugovc, C.; Mereiter, K.; Zobetz, E.; Schmid, R.; Kirchner, K.
Organometallics 1996, 15, 5275-5277.
(17) For precedents of transition metal-promoted 1,2-silyl migra-
tion of silylacetylenes to give â-silylvinylidene complexes, see: (a)
Werner, H.; Baum M.; Schneider, D.; Windmu¨ller, B. Organometallics
1994, 13, 1089-1097. (b) Katayama, H.; Onitsuka, K.; Ozawa, F.
Organometallics 1996, 15, 4642-4645. (c) Connelly, N. G.; Geiger,
W. E.; Lagunas, M. C.; Metz, B.; Rieger, A. L.; Rieger, P. H.; Shaw, M.
J . J . Am. Chem. Soc. 1995, 117, 12202-12208. (d) Sakurai, H.;
Fujii, T.; Sakamoto, K. Chem. Lett. 1992, 339-342. (e) Naka, A.;
Okazaki, S.; Hayashi, M.; Ishikawa, M. J . Organomet. Chem. 1995,
499, 35-41.
1
Chemical shifts are reported in δ (ppm), referenced to the H
(of residual protons) and 13C signals of deuterated solvents or
(18) (a) de los R´ıos, I.; J ime´nez, T.; Puerta, C.; Valerga, P. J . Am.
Chem. Soc. 1997, 119, 6529-6538. (b) Gamasa, M. P.; Gimeno, J .;
Lastra, E.; Lanfranchi, M.; Tiripicchio, A. J . Organomet. Chem. 1992,
430, C39-C43. (c) Bruce, M. I.; Swincer, A. G. Aust. J . Chem. 1980,
33, 1471-1483.

5194 Organometallics, Vol. 17, No. 23, 1998
Katayama and Ozawa
to the 31P signal of external 85% H3PO4. Infrared spectra were
recorded at room temperature on a J ASCO FT/IR-410 instru-
ment.
overnight. Complexes 3a -e could be crystallized by slow
diffusion of MeOH into CH2Cl2 solutions at -20 °C.
Ru Cl2{dCdC(H)Bu t}(P P r i3)2 (3b): brown solid (57%, from
1
4
1; 96%, from 2); H NMR (CDCl3, 23 °C) δ 3.06 (t, J PH ) 3.6
Hz, 1H, dCdCH), 2.97-2.85 (m, 6H, PCHCH3), 1.40 (doublet
of virtual triplets, 3J HH ) 5.8 Hz, J ) 6.6 Hz,22 36H, PCHCH3),
1.10 (s, 9H, t-Bu); 13C{1H} NMR (CDCl3, 23 °C) δ 337.1 (t, 2J PC
Toluene, benzene, THF, and hexane were dried over sodium
benzophenone ketyl. Methanol was dried with Mg(OMe)2.
CH2Cl2 and acetonitrile were dried over CaH2. These solvents
were distilled and stored over activated molecular sieves
(MS4A) under an argon atmosphere. CDCl3, CD2Cl2, and
benzene-d6 were dried over MS4A, vacuum transferred, and
stored under a nitrogen atmosphere in the dark. Ru(methallyl)2-
3
) 15 Hz, RudCdC), 115.5 (t, J PC ) 5 Hz, RudCdC), 32.1 (s,
C(CH3)3), 23.1 (virtual triplet, J ) 9 Hz,22 PCHCH3), 20.1 (s,
PCHCH3); 31P{1H} NMR (CDCl3, 23 °C) δ 27.1 (s). Anal. Calcd
for C24H52Cl2P2Ru: C, 50.17; H, 9.12. Found: C, 49.96; H,
9.08.
(cod),9 [RuCl2(p-cymene)]2,10 PPri ,19 ferrocenylacetylene,20
3
p-MeO2CC6H4CtCH,21 p-MeOC6H4CtCH,21 and 1,1′-bis{(tri-
methylsilyl)ethynyl}ferrocene20 were prepared according to the
literature. Liquid alkynes were degassed by three freeze-
pump-thaw cycles prior to use. All other compounds were
obtained from commercial sources and used without purifica-
tion.
Ru Cl2{dCdC(H)F c}(P P r i3)2 (3c): brown solid (67% from
4
2); 1H NMR (CDCl3, 23 °C) δ 4.16 (t, J PH ) 3.3 Hz, 1H, dCd
CH), 4.06 (s, 5H, C5H5), 4.04, 3.92 (each apparent triplet, J )
1.8 Hz, 2H, C5H4), 2.90-2.78 (m, 6H, PCHCH3), 1.36 (doublet
of virtual triplets, 3J HH ) 6.0 Hz, J ) 7.1 Hz,22 36H, PCHCH3);
2
13C{1H} NMR (CDCl3, 23 °C) δ 338.6 (t, J PC ) 15 Hz, Rud
Syn th esis of Vin ylid en e Com p lexes 3a -e a n d 4a -c.
(a ) F r om Ru (m eth a llyl)2(cod ) (1). To a colorless solution
of 1 (202 mg, 0.632 mmol) in CH2Cl2 (25 mL) and acetone (16
3
CdC), 103.2 (t, J PC ) 4 Hz, RudCdC), 78.6 (s, C1 of C5H4),
68.7 (s, C5H5), 66.9, 66.2 (each s, C5H4), 23.2 (virtual triplet, J
) 9 Hz,22 PCHCH3), 20.1 (s, PCHCH3); 31P{1H} NMR (CDCl3,
23 °C) δ 29.8 (s). Anal. Calcd for C30H52Cl2P2FeRu: C, 51.29;
H, 7.46. Found: C, 51.19; H, 7.46.
Ru Cl2{dCdC(H)C6H4CO2Me-p}(P P r i3)2 (3d ): brown solid
(52% from 2). An analytically pure compound containing 1
equiv of CH2Cl2 in the crystal was obtained by recrystallization
from CH2Cl2/MeOH (18% yield). IR (KBr): 1716 (νCdO), 1580
mL) was added PPri (201 mg, 1.25 mmol) at room tempera-
3
ture. The mixture was cooled to -20 °C, and a solution of HCl
in MeOH (1.7 M, 0.74 mL, 1.3 mmol) was added dropwise. The
solution instantly turned yellow, and then a yellow precipitate
gradually formed from the solution. After the mixture was
stirred for 30 min at -20 °C, the precipitate was collected by
filtration, washed with cold pentane, and dried under vacuum
at low temperature (<-20 °C). Since the product was ther-
mally unstable, its elemental analysis was infeasible, but the
(νCdC) cm-1
.
1H NMR (C6D6, 19 °C): δ 8.15, 7.17 (each d, J )
4
8.8 Hz, 2H, C6H4), 4.69 (t, J PH ) 3.4 Hz, 1H, dCdCH), 4.24
(s, 2H, CH2Cl2), 3.48 (s, 3H, CO2CH3), 2.80-2.68 (m, 6H,
PCHCH3), 1.25 (doublet of virtual triplets, 3J HH ) 6.4 Hz, J )
6.4 Hz,22 36H, PCHCH3). 13C{1H} NMR (C6D6, 19 °C): δ 338.0
NMR data clearly indicated the formation of [RuCl2(PPri )2]n.
3
1H NMR (CD2Cl2, -30 °C): δ 2.82-2.70 (m, 6H, PCHCH3),
2
3
1.45 (dd, J PH ) 16.8 Hz, J HH ) 7.1 Hz, 36H, PCHCH3).
2
(t, J PC ) 15 Hz, RudCdC), 166.7 (s, CO2CH3), 140.1 (s, C4
13C{1H} NMR (CD2Cl2, -30 °C): δ 19.0 (d, J PC ) 40 Hz,
1
of C6H4), 130.2 (s, C3,5 of C6H4), 126.1 (s, C1 of C6H4), 124.8
PCHCH3), 17.7 (s, PCHCH3). 31P{1H} NMR (CD2Cl2, -30
°C): δ 35.6 (s).
(s, C2,6 of C6H4), 108.8 (t, J PC ) 5 Hz, RudCdC), 53.0 (s,
3
CH2Cl2), 51.2 (s, CO2CH3), 23.7 (virtual triplet, J ) 9 Hz,22
PCHCH3), 20.0 (s, PCHCH3). 31P{1H} NMR (C6D6, 19 °C): δ
30.3 (s). Anal. Calcd for C28H50Cl2O2P2Ru‚CH2Cl2: C, 47.23;
H, 7.11. Found: C, 47.83; H, 7.18.
The reactions with alkynes were performed without isolation
of [RuCl2(PPri )2]n. To a suspension of [RuCl2(PPri )2]n, which
3
3
was prepared from 1 (248 mg, 0.777 mmol), PPri (249 mg,
3
1.55 mmol), and a MeOH solution of HCl (1.7 M, 0.94 mL, 1.6
mmol) in CH2Cl2 (30 mL) and acetone (20 mL), was added
PhCtCH (0.80 g, 7.8 mmol) in one portion at -20 °C. On
being stirred at room temperature, the heterogeneous mixture
gradually turned to a deep purple homogeneous solution. After
16 h, the solution was concentrated to dryness by pumping,
and the resulting solid was washed with MeOH (6 mL × 3) at
-20 °C to give a brown microcrystalline solid of 3a (279 mg,
61%). The NMR data were identical with those reported.8
Similarly, 3b was obtained with tert-butylacetylene in place
of phenylacetylene in 57% yield.
Ru Cl2{dCdC(H)C6H4OMe-p}(P P r i
)
(3e): dark green
2
3
solid (63% from 2); 1H NMR (CDCl3, 19 °C): δ 6.89, 6.73 (each
d, J ) 8.8 Hz, 2H, C6H4), 4.50 (t, 4J PH ) 3.4 Hz, 1H, dCdCH),
3.75 (s, 3H, OCH3), 2.90-2.81 (m, 6H, PCHCH3), 1.35 (doublet
of virtual triplets, 3J HH ) 6.4 Hz, J ) 6.6 Hz,22 36H, PCHCH3).
2
13C{1H} NMR (CDCl3, 19 °C) δ 344.6 (t, J PC ) 15 Hz, Rud
CdC), 156.4 (s, C4 of C6H4), 126.1 (s, C3,5 of C6H4), 124.4 (s, C1
3
of C6H4), 113.6 (s, C2,6 of C6H4), 108.2 (t, J PC ) 5 Hz, RudCd
C), 55.2 (s, OCH3), 23.3 (virtual triplet, J ) 8 Hz,22 PCHCH3),
20.0 (s, PCHCH3); 31P{1H} NMR (CDCl3, 19 °C) δ 28.7 (s). Anal.
Calcd for C27H50Cl2OP2Ru: C, 51.92; H, 8.07. Found: C, 51.98;
H, 8.11.
(b) F r om [Ru Cl2(p-cym en e)]2 (2). A typical procedure is
as follows. To a suspension of 2 (205 mg, 0.335 mmol) in
Ru Cl2{dCdC(H)P h }(P Cy3)2 (4a ): dark purple solid (87%
toluene (11 mL) was added PPri (214 mg, 1.34 mmol) with
from 2); 1H NMR (C6D6, 60 °C) δ 7.18-7.09, 7.03-6.98, 6.89-
3
stirring at room temperature. The mixture instantly changed
into a reddish brown solution. PhCtCH (68 mg, 0.67 mmol)
was added, and the solution was heated at 80 °C for 26 h with
stirring. The solution gradually darkened. Volatile materials
were thoroughly removed by pumping, and the resulting oily
product was washed with MeOH (2 mL × 3) at -70 °C to give
a brown microcrystalline solid of 3a (386 mg, 97%), which was
analytically pure. All complexes listed in Scheme 2 were
similarly prepared. Complex 3b was prepared using an excess
amount (10 equiv/Ru) of t-BuCtCH; otherwise the yield
considerably lowered. Complexes 4a -c could be isolated as
crystals simply by cooling the reaction solutions at -20 °C
4
6.84 (each m, 5H, Ph), 4.70 (t, J PH ) 3.6 Hz, 1H, dCdCH),
2.88-2.75, 2.30-2.15, 1.82-1.50, 1.30-1.08 (each m, 66H,
2
Cy); 13C{1H} NMR (C6D6, 60 °C) δ 342.1 (t, J PC ) 14 Hz,
RudCdC), 133.9 (s, C1 of Ph), 128.5, 125.8, 124.1 (each s, C2-6
3
of Ph), 109.6 (t, J PC ) 5 Hz, RudCdC), 34.0 (virtual triplet,
J ) 8 Hz,22 C1 of Cy), 30.7 (s, C3,5 of Cy), 28.3 (s, C2,6 of Cy),
27.0 (s, C4 of Cy); 31P{1H} NMR (C6D6, 60 °C) δ 22.5 (s). Anal.
Calcd for C44H72Cl2P2Ru; C, 63.29; H, 8.69. Found; C, 63.49;
H, 8.42.
Ru Cl2{dCdC(H)Bu t}(P Cy3)2 (4b): purple solid (63% from
4
2); 1H NMR (CDCl3, 20 °C) δ 2.84 (t, J PH ) 3.6 Hz, 1H, dCd
CH), 2.70-2.56, 2.15-2.04, 1.88-1.56, 1.34-1.16 (each m,
66H, Cy), 1.07 (s, 9H, t-Bu); 13C{1H} NMR (CDCl3, 20 °C) δ
2
3
338.5 (t, J PC ) 14 Hz, RudCdC), 114.7 (t, J PC ) 5 Hz, Rud
CdC), 33.1 (virtual triplet, J ) 9 Hz,22 C1 of Cy), 32.3 (s,
C(CH3)3), 32.0 (s, C3,5 of Cy), 30.1 (s, C(CH3)3), 27.9 (virtual
(19) Cowley, A. H.; Mills, J . L. J . Am. Chem. Soc. 1969, 91, 2915-
2919.
(20) Doisneau, G.; Balavoine, G.; Fillebeen-Khan, T. J . Organomet.
Chem. 1992, 425, 113-117.
(21) Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N.
Synthesis 1980, 627-630.
(22) Apparent coupling constant for the virtual triplet signal.

Convenient Routes to Vinylideneruthenium Dichlorides
Organometallics, Vol. 17, No. 23, 1998 5195
Ta ble 2. Cr ysta llogr a p h ic Da ta a n d Str u ctu r e Refin em en t for 3a , 4a , a n d 5
3a
4a
5
formula
fw
C
26H48Cl2P2Ru
C44H72Cl2P2Ru‚CH2Cl2
919.91
C22H48N2Cl2P2Ru
574.56
594.59
cryst size, mm
cryst syst
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
0.4 × 0.3 × 0.3
monoclinic
P21/a (No. 14)
24.363(3)
9.721(3)
28.088(3)
0.4 × 0.2 × 0.2
triclinic
P1h (No. 2)
13.923(2)
14.353(2)
13.168(3)
110.07(2)
112.61(1)
76.08(1)
2263.7(7)
2
0.5 × 0.4 × 0.1
monoclinic
P21/n (No. 14)
11.248(2)
8.593(1)
14.969(1)
115.660(6)
104.250(8)
5996(2)
8
1.317
8.20
1402.2(3)
2
1.361
8.75
Z
d
calcd, g cm-3
1.350
6.83
972
µ(Mo KR), cm-1
F(000)
2496
604
2θ range, deg
temp, K
5.0-55.0
296
5.0-55.0
198
5.0-55.0
198
transm factors
no. of rflns collcd
no. of unique rflns
no. of obsd rflns
no. of variables
Ra
0.96-1.00
14229
13748 (Rint ) 0.032)
8415 (I g 3σ(I))
559
0.033
0.034
1.39
0.92-1.00
10808
10378 (Rint ) 0.025)
8556 (I g 3σ(I))
469
0.033
0.053
1.22
0.80-1.00
3386
3226 (Rint ) 0.036)
2827 (I g 3σ(I))
134
0.025
0.034
2.12
b
Rw
GOFc
max ∆/σ in final cycle
0.06
0.30, -0.33
0.00
1.15, -0.94
0.01
0.44, -0.65
max and min peak, e Å-3
a
b
2
R ) ∑||Fo| - |Fc||/∑|Fo|. Rw ) [∑w(|Fo| - |Fc|)2/∑w|Fo| ]1/2, w ) 1/[σ2(Fo)]. c GOF ) [∑w(|Fo| - |Fc|)2/(No - Np)]1/2
.
triplet, J ) 5 Hz,22 C2,6 of Cy), 26.7 (s, C4 of Cy). 31P{1H} NMR
(CDCl3, 20 °C) δ 17.9 (s). Anal. Calcd for C42H76Cl2P2Ru: C,
61.90; H, 9.40. Found: C, 61.73; H, 9.29.
Syn th esis of Ru Cl2{dCdC(SiMe3)P h }(P Cy3)2 (6). To a
suspension of 2 (100 mg, 0.163 mmol) in toluene (5 mL) were
added PCy3 (185 mg, 0.659 mmol) and PhCtCSiMe3 (580 mg,
3.33 mmol) at room temperature. The mixture was stirred at
60 °C for 51 h. The initially deep purple solution gradually
darkened. The resulting solution was allowed to stand at -30
°C for 1 day to give dark purple crystals of 6, which was
collected by filtration and dried under vacuum (90 mg). The
filtrate was concentrated to dryness, and the resulting solid
was recrystallized from CH2Cl2/MeOH to give second crop of
6 (88 mg; totally 60%). 1H NMR (CDCl3, 18 °C): δ 7.28-7.09,
6.90-6.85 (each m, 5H, Ph), 2.70-2.60, 2.10-2.08, 1.82-1.49,
1.30-1.10 (each m, 66H, Cy), 0.29 (s, 9H, SiMe3). 13C{1H}
NMR (CDCl3, 18 °C): δ 330.1 (t, 2J PC ) 12 Hz, RudCdC), 135.8
(s, C1 of Ph), 129.0, 128.2, 127.5 (each s, C2-6 of Ph), 108.2 (br
s, RudCdC), 33.0 (virtual triplet, J ) 8 Hz,22 C1 of Cy), 30.1
(s, C3,5 of Cy), 27.9 (s, C2,6 of Cy), 26.6 (s, C4 of Cy), 1.88 (s,
SiMe3). 31P{1H} NMR (CDCl3, 18 °C): δ 20.6 (s). Anal. Calcd
for C47H80Cl2P2SiRu: C, 62.23; H, 8.89. Found: C, 61.97; H,
8.78.
Ru Cl2{dCdC(H)F c}(P Cy3)2 (4c): deep purple solid (91%
1
4
from 2); H NMR (C6D6, 17 °C) δ 4.25 (t, J PH ) 3.2 Hz, 1H,
dCdCH), 4.17 (s, 5H, C5H5), 4.09, 4.05 (each apparent triplet,
J ) 1.6 Hz, 2H, C5H4), 2.88-2.75, 2.30-2.16, 1.85-1.58, 1.35-
1.15 (each m, 66H, Cy); 13C{1H} NMR (C6D6, 17 °C) δ 338.3 (t,
2J PC ) 14 Hz, RudCdC), 103.3 (br, RudCdC), 79.2 (s, C1 of
C5H4), 69.2 (s, C5H5), 67.6, 66.8 (each s, C2,5 and C3,4 of C5H4),
33.5 (virtual triplet, J ) 8 Hz,22 C1 of Cy), 30.6 (s, C3,5 of Cy),
28.2 (s, C2,6 of Cy), 26.9 (s, C4 of Cy). 31P{1H} NMR (C6D6, 17
°C) δ 21.8 (s). Anal. Calcd for C48H76Cl2P2FeRu‚0.5C7H8: C,
62.55; H, 8.15. Found: C, 62.48, H, 8.07.
Syn th esis of Ru Cl2(P P r i3)2(NCMe)2 (5). To a suspension
of 2 (202 mg, 0.330 mmol) in toluene (11 mL) were added
MeCN (0.34 mL, 6.5 mmol) and PPri (212 mg, 1.32 mmol) at
3
room temperature. The reaction mixture was stirred at 80
°C for 16 h. The initially reddish brown solution gradually
turned heterogeneous to give orange precipitate of 5, which
was collected by filtration using a filter-paper-tipped cannula,
washed with hexane (3 mL × 3), and dried under vacuum (283
Syn th esis of 7. To a suspension of 2 (204 mg, 0.333 mmol)
in toluene (11 mL) were added PPri3 (214 mg, 1.34 mmol) and
1,1′-bis{(trimethylsilyl)ethynyl}ferrocene (127 mg, 0.336 mmol)
at room temperature. The mixture was stirred at 80 °C for
35 h. The initially reddish brown solution gradually turned
dark purple. Volatile materials were removed by pumping,
and the resulting solid was washed with MeOH (3 mL × 3) to
give a dark purple microcrystalline solid of 7 (418 mg, 92%),
which was spectroscopically pure. Analytically pure compound
containing 1 equiv of CH2Cl2 in the crystal was obtained by
recrystallization from CH2Cl2 (71% yield). 1H NMR (CDCl3,
19 °C): δ 5.30 (s, 2H, CH2Cl2), 4.02-3.88 (m, 8H, C5H4), 2.94-
2.73 (m, 12H, PCHCH3), 1.35 (doublet of virtual triplets, 3J HH
) 6.4 Hz, J ) 6.4 Hz,22 72H, PCHCH3), 0.30 (s, 18H, SiMe3).
mg, 75%). IR (KBr): 2265 (νCN) cm-1
.
1H NMR (CDCl3, 23
°C): δ 2.93-2.81 (m, 6H, PCHCH3), 2.37 (virtual triplet, J )
1.2 Hz,22 6H, CH3CN), 1.41 (doublet of virtual triplets, 3J HH
)
6.3 Hz, J ) 6.0 Hz,22 36H, PCHCH3). 13C{1H} NMR (CDCl3,
23 °C): δ 124.9 (s, CH3CN), 23.3 (virtual triplet, J ) 8 Hz,22
PCHCH3), 19.8 (s, PCHCH3), 5.5 (s, CH3CN). 31P{1H} NMR
(CDCl3, 23 °C): δ 21.9 (s). Anal. Calcd for C22H48N2Cl2P2Ru:
C, 45.99; H, 8.42; N, 4.88. Found: C, 45.87; H, 8.40; N, 4.93.
Rea ction of 5 w ith Alk yn es. To a suspension of 5 (63
mg, 0.11 mmol) in CH2Cl2 (2.7 mL) was added PhCtCH (12
mg, 0.12 mmol). The reaction mixture was stirred at 40 °C
for 20 h. As the reaction proceeded the yellow suspension
gradually turned to a dark purple solution. The resulting
solution was concentrated to dryness by pumping. 1H and
31P{1H} NMR analysis of the resulting solid revealed the
selective formation of 3a . The reactions of 5 with tert-
butylacetylene and ferrocenylacetylene were similarly exam-
ined, where 3b,c were formed in quantitative yields as
confirmed by NMR spectroscopy.
2
13C{1H} NMR (CDCl3, 19 °C): δ 325.7 (t, J PC ) 14 Hz,
RudCdC), 102.9 (s, RudCdC), 84.2 (s, C1 of C5H4), 68.4, 66.9
(each s, C2,5 and C3,4 of C5H4), 54.0 (s, CH2Cl2), 23.1 (virtual
triplet, J ) 9 Hz,22 PCHCH3), 20.3 (s, PCHCH3), 2.5 (s, SiMe3).
31P{1H} NMR (CDCl3, 19 °C): δ 29.4 (s). Anal. Calcd for
C
56H110Cl4FeP4Si2Ru2‚CH2Cl2: C, 47.27; H, 7.79. Found: C,
47.27; H, 7.79.

5196 Organometallics, Vol. 17, No. 23, 1998
Katayama and Ozawa
Rea ction of [Ru Cl2(P P r i3)2]n w ith F cC≡CSiMe3. The
with an epoxy resin adhesive. All measurements were per-
formed on a Rigaku AFC7R four-circle diffractometer with
graphite-monochromated Mo KR radiation (λ ) 0.710 69 Å).
Unit cell dimensions were obtained from a least-squares
refinement of the setting angles of automatically centered 25
reflections in the range 25° e 2θ e 30° for each crystal.
Diffraction data were collected in the range 5.0 < 2θ < 55.0°
using the ω-2θ scan technique at a scan rate of 16.0°/min in
ω. The data were corrected for Lorentz and polarization
effects, decay (based on three standard reflections monitored
at every 150 reflection measurements), and absorption (em-
pirical, based on azimuthal scans of three reflections).
All calculations were performed with the TEXSAN crystal
structure analysis package provided by Rigaku Corp., Tokyo,
J apan.23 The scattering factors were taken from the Interna-
tional Tables for X-ray Crystallography.24 The structure was
solved by heavy-atom Patterson methods (PATTY) and ex-
panded using Fourier techniques (DIRDIF94). The structures
were refined by full-matrix least-squares with anisotropic
thermal parameters for all non-hydrogen atoms. In the final
cycles of refinement, hydrogen atoms with isotropic temper-
ature factors (Biso ) 1.20Bbonded atom) were located at idealized
positions (d(C-H) ) 0.95 Å) and were included in calculations
without refinement of their parameters.
precipitate of [RuCl2(PPri )2]n, formed from 1 (23.3 mg, 72.9
3
µmol) in CH2Cl2 and acetone (vide supra), was filtered out,
washed with cold pentane, and dried under vacuum. The
complex was suspended in CH2Cl2 (2 mL) at -20 °C, and FcCt
CSiMe3 (207 mg, 0.732 mmol) was added. The mixture was
stirred at room temperature for 4 h. GC-MS analysis of the
dark orange solution showed the formation of Me3SiOH. The
solution was concentrated to dryness by pumping to give a
1
dark brown solid. The H and 31P{1H} NMR spectra indicated
the formation of 3c in 67% selectivity, along with some
unidentified ruthenium species.
Rea ction of [Ru Cl2(P P r i3)2]n w ith Me3SiC≡CH. The
complex [RuCl2(PPri )2]n prepared from 1 (201 mg, 0.629
3
mmol) similarly to the above experiment was suspended in
CH2Cl2 (16 mL) at -20 °C, and Me3SiCtCH (0.62 g, 6.3
mmol) was added in one potion. The mixture was stirred at
room temperature for 30 min. The dark purple solution was
concentrated to dryness by pumping, and the resulting
solid was recrystallized from CH2Cl2/MeOH to give deep
red crystals of RuMeCl(CO)(PPri )2 (8) (47 mg, 15%). The
3
product was spectroscopically pure, but did not provide
satisfactory elemental analysis. IR (KBr): 1893 (νCO) cm-1
.
1H NMR (CDCl3, 23 °C): δ 2.79-2.67 (m, 6H, PCHCH3), 1.28
(doublet of virtual triplets, 3J HH ) 7.1 Hz, J ) 13.2 Hz,22 36H,
3
PCHCH3), 1.19 (t, J HP ) 4.9 Hz, 3H, RuCH3). 13C{1H} NMR
Su p p or tin g In for m a tion Ava ila ble: Details of the struc-
ture determinations of 3a , 4a , and 5, including figures giving
the atomic numbering schemes and tables of atomic coordi-
nates, thermal parameters, and complete bond distances and
angles (27 pages). Ordering information is given on any
current masthead page.
2
(CDCl3, 23 °C): δ 202.0 (t, J PC ) 14 Hz, CO), 24.0 (virtual
triplet, J ) 9 Hz,22 PCHCH3), 20.1, 19.8 (each s, PCHCH3),
2
-13.4 (t, J PC ) 7 Hz, RuCH3). 31P{1H} NMR (CDCl3, 23 °C):
δ 36.6 (s).
X-r a y Cr ysta llogr a p h ic Stu d ies. Single crystals of 3a
and 5 suitable for X-ray diffraction study were obtained by
recrystallization from Et2O and toluene, respectively. The
crystal of 4a was grown by slow diffusion of the CH2Cl2
solution into MeOH at -20 °C. The crystal data and details
of data collection and structure refinement are summarized
in Table 2. Crystals were mounted on a glass fiber and fixed
OM980582H
(23) TEXSAN Structure Analysis Package, Molecular Structure
Corp., 1985 and 1992.
(24) Cromer, D. T.; Waber, J . T. International Tables for X-ray
Crystallography; The Kynoch Press: Birmingham, U.K., 1974; Vol. IV.