Influence of the group 14 element on the deprotonation of OsH(η5-C5H5)(C≡CPh) (EPh3) (PiPr3) (E = Si, Ge): Two different organometallic chemistries

Article abstract of DOI:10.1021/om010504l

The complexes OsH(η⁵-C₅H₅)Cl(EPh₃) (PⁱPr₃) (E = Si (1), Ge (2)) react with lithium phenylacetylide to give the hydride-alkynyl derivatives OsH(η⁵-C₅H₅)(C≡CPh)(EPh₃) (PⁱPr₃) (E = Si (3), Ge (4)). The structure of 4 has been determined by X-ray diffraction analysis. The distribution of ligands around the osmium atom can be described as a four-legged piano-stool geometry with the monodentate ligands lying in the four-membered face. Treatment of 3 with n-butyllithium and the subsequent addition of methanol, methanol-d₄, and methyl iodide to the resulting solutions leads to OsH(η⁵-C₅H₄SiPh₃){=C=C(H)Ph} (PⁱPr₃) (5), OsH(η⁵-C₅H₄SiPh₃){=C=C(D)Ph} (PⁱPr₃) (5-d), and OsH(η⁵-C₅H₄SiPh₃) {o-C₆H₄C(CH₃)=CH}- (PⁱPr₃) (6), respectively. Similarly to 3, the reaction of the perdeuterated cyclopentadienyl complex OsH(η⁵-C₅D₅)(C≡CPh)(SiPh₃) (PⁱPr₃) (3-d₅) with n-butyllithium and methanol gives OsH(η⁵-C₅D₄SiPh₃) {=C=C(H)Ph}(PⁱPr₃) (5-d₄). The structure of 6 has been also determined by X-ray diffraction analysis. In this case, the distribution of ligands around the osmium atom can be described as a piano-stool geometry with the metalated carbon atom transoid to the phosphine and cisoid to the hydride. Complex 5 reacts with HBF₄ to give the hydride-carbyne derivative [OsH(η⁵-C₅H₄SiPh₃) (≡CCH₂Ph)(PⁱPr₃)] BF₄ (7), which is stable. Initially, the addition of HBF₄ to diethyl ether solutions of 6 also leads to a hydride-carbyne complex, [OsH(η⁵-C₅H₄SiPh₃) {≡CCH(CH₃)Ph}(PⁱPr₃)]BF₄ (8). However, in solution, complex 8 evolves into the hydride-allyl compound [OsH(η⁵-C₅H₄SiPh₃) {η³-CH₂C(Ph)CH₂}(Pⁱ Pr₃)]BF₄ (9). The structure of 9 has been determined by X-ray diffraction analysis. The distribution of ligands around the osmium atom can be described as a piano-stool geometry, where the allyl ligand occupies two cisoid positions. Treatment of 4 with n-butyllithium and the subsequent addition of methanol, methanol-d₄, and methyl iodide to the resulting solution gives the germyl-vinylidene complexes Os(η⁵-C₅H₅)(GePh₃) {=C=C(H)Ph}(PⁱPr₃) (10), Os(η⁵-C₅H₄D)(GePh₃) {=C=C(D)Ph}(PⁱPr₃) (10-d₂), and Os(η⁵-C₅H₄CH₃)(GePh₃) {=C=C(CH₃)Ph} (PⁱPr₃) (11), respectively. The protonation of 10 and 11 with HBF₄ affords the corresponding carbyne derivatives [Os(η⁵-C₅H₅)(GePh₃) (≡CCH₂Ph)(PⁱPr₃)] BF₄ (12) and [Os(η⁵-C₅H₄CH₃) (GePh₃){≡CCH(CH₃)Ph} (PⁱPr₃)] BF₄ (13).

Full text of DOI:10.1021/om010504l

Organometallics 2001, 20, 4875-4886
4875
In flu en ce of th e Gr ou p 14 Elem en t on th e Dep r oton a tion
of OsH(η5-C5H5)(CtCP h )(EP h 3)(P iP r 3) (E ) Si, Ge): Tw o
Differ en t Or ga n om eta llic Ch em istr ies
Miguel Baya, Miguel A. Esteruelas,* and Enrique On˜ate
Departamento de Quı´mica Inorga´nicasInstituto de Ciencia de Materiales de Arago´n,
Universidad de ZaragozasCSIC, 50009 Zaragoza, Spain
Received J une 11, 2001
The complexes OsH(η5-C5H5)Cl(EPh3)(PiPr3) (E ) Si (1), Ge (2)) react with lithium
phenylacetylide to give the hydride-alkynyl derivatives OsH(η5-C5H5)(CtCPh)(EPh3)(Pi-
Pr3) (E ) Si (3), Ge (4)). The structure of 4 has been determined by X-ray diffraction analysis.
The distribution of ligands around the osmium atom can be described as a four-legged piano-
stool geometry with the monodentate ligands lying in the four-membered face. Treatment
of 3 with n-butyllithium and the subsequent addition of methanol, methanol-d4, and methyl
iodide to the resulting solution leads to OsH(η5-C5H4SiPh3){dCdC(H)Ph}(PiPr3) (5), OsH-
(η5-C5H4SiPh3){dCdC(D)Ph}(PiPr3) (5-d ), and OsH(η5-C5H4SiPh3){o-C6H4C(CH3)dCH}-
(PiPr3) (6), respectively. Similarly to 3, the reaction of the perdeuterated cyclopentadienyl
complex OsH(η5-C5D5)(CtCPh)(SiPh3)(PiPr3) (3-d 5) with n-butyllithium and methanol gives
OsH(η5-C5D4SiPh3){dCdC(H)Ph}(PiPr3) (5-d 4). The structure of 6 has been also determined
by X-ray diffraction analysis. In this case, the distribution of ligands around the osmium
atom can be described as a piano-stool geometry with the metalated carbon atom transoid
to the phosphine and cisoid to the hydride. Complex 5 reacts with HBF4 to give the hydride-
carbyne derivative [OsH(η5-C5H4SiPh3)(tCCH2Ph)(PiPr3)]BF4 (7), which is stable. Initially,
the addition of HBF4 to diethyl ether solutions of 6 also leads to a hydride-carbyne complex,
[OsH(η5-C5H4SiPh3){tCCH(CH3)Ph}(PiPr3)]BF4 (8). However, in solution, complex 8 evolves
into the hydride-allyl compound [OsH(η5-C5H4SiPh3){η3-CH2C(Ph)CH2}(PiPr3)]BF4 (9). The
structure of 9 has been determined by X-ray diffraction analysis. The distribution of ligands
around the osmium atom can be described as a piano-stool geometry, where the allyl ligand
occupies two cisoid positions. Treatment of 4 with n-butyllithium and the subsequent addition
of methanol, methanol-d4, and methyl iodide to the resulting solution gives the germyl-
vinylidene complexes Os(η5-C5H5)(GePh3){dCdC(H)Ph}(PiPr3) (10), Os(η5-C5H4D)(GePh3)-
{dCdC(D)Ph}(PiPr3) (10-d 2), and Os(η5-C5H4CH3)(GePh3){dCdC(CH3)Ph}(PiPr3) (11), re-
spectively. The protonation of 10 and 11 with HBF4 affords the corresponding carbyne
derivatives [Os(η5-C5H5)(GePh3)(tCCH2Ph)(PiPr3)]BF4 (12) and [Os(η5-C5H4CH3)(GePh3)-
{tCCH(CH3)Ph}(PiPr3)]BF4 (13).
In tr od u ction
The acidity of the hydride ligand in the hydride-
alkynyl intermediates appears to be the key for the
π-alkyne-vinylidene transformation by 1,3-hydrogen
shift. For group 8, Puerta and co-workers3 have proved
that half-sandwich ruthenium-vinylidene compounds
can be formed from hydride-alkynyl species in a
dissociative two-step process (elimination-addition).
The first step consists of the dissociation of a proton,
and the second one is the protonation of the resulting
alkynyl intermediate.
Transition-metal hydride complexes are involved in
many stoichiometric and catalytic processes.1 Therefore,
a knowledge of the chemical properties of the metal-
hydrogen bonds is of great interest. Of these, acid-base
properties are among the most important and funda-
mental. They depend on the electron density of the
metallic fragment. For a given metal, the electron
density is modulated by the coligands.2
In many cases the hydride complex bears a cyclopen-
tadienyl ligand, which is known to have rather acidic
C-H bonds. In agreement with the acidity of the η5-
C5H5 group, cyclopentadienyl complexes of molybdenum,
(1) (a) Transition Metal Hydrides; Dedieu, A., Ed.; VCH: New York,
1992. (b) Chaloner, P. A.; Esteruelas, M. A.; J oo´, F.; Oro, L. A.
Homogeneous Hydrogenation; Kluwer Academic: Dordrecht, The
Netherlands, 1994. (c) Esteruelas, M. A.; Lo´pez, A. M. Ruthenium- and
Osmium-hydride compounds containing triisopropylphosphine as pre-
cursors for carbon-carbon and carbon-heteroatom coupling reactions.
In Recent Advances in Hydrides Chemistry; Peruzzini, M., Poli, R., Eds.,
Elsevier: Amsterdam, in press.
(3) (a) De Los R´ıos, I.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga,
P. J . Am. Chem. Soc. 1997, 119, 6529. (b) Bustelo, E.; J ime´nez-Tenorio,
M.; Puerta, M. C.; Valerga, P. Organometallics 1999, 18, 950. (c)
Bustelo, E.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P. Organo-
metallics 1999, 18, 4563. (d) Puerta, M. C.; Valerga, P. Coord. Chem.
Rev. 1999, 193-195, 977.
(2) (a) Angelici, R. J . Acc. Chem. Res. 1995, 28, 51. (b) Abdur-Rashid,
K.; Fong, T. P.; Greaves, B.; Gusev, D. G.; Hinman, J . G.; Landau, S.
E.; Lough, A. J .; Morris, R. H. J . Am. Chem. Soc. 2000, 122, 9155.
10.1021/om010504l CCC: $20.00 © 2001 American Chemical Society
Publication on Web 10/02/2001

4876 Organometallics, Vol. 20, No. 23, 2001
Baya et al.
tungsten,4 rhenium,5 iron,6 and ruthenium7 undergo
base-induced migration reactions of a monodentate
ligand from the metal to a neighboring cyclopentadienyl
carbon atom. It is widely accepted that such reactions
involve the initial deprotonation of the cyclopentadienyl
ring followed by the ligand migration. The produced
anion is quenched by reaction with an electrophile.
Despite the known kinetic inertia of the Os(η5-C5R5)-
L3 species,8 we have previously reported that the com-
plex Os(η5-C5H5)Cl(PiPr3)2 reacts with HER3 molecules
to afford the osmium(IV)-hydride derivatives OsH(η5-
C5H5)Cl(ER3)(PiPr3) (E ) Si, Ge).9 The nature of E has
a marked influence on the reactivity of these types of
compounds. Treatment of OsH(η5-C5H5)Cl(EPh3)(PiPr3)
with alkyllithium reagents produces the replacement of
the chlorine ligand by the alkyl group, to afford OsH-
(η5-C5H5)(EPh3)R(PiPr3). These intermediates are un-
stable and evolve into two different types of substituted
cyclopentadienyl complexes, depending on the nature
of E.10 The intermediates OsH(η5-C5H5)(GePh3)R(PiPr3)
afford the dihydride-germyl derivatives OsH2(η5-
F igu r e 1. Molecular diagram of the complex OsH(η5-
C5H5)(CtCPh)(GePh3)(PiPr3) (4).
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for th e Com p lex
OsH(η5-C5H5)(CtCP h )(GeP h 3)(P iP r 3) (4)
s
C5H4R)(GePh3)(PiPr3) (R ) CH3, nBu, Bu) by R(Os)/
Os-Ge
2.5033(4)
2.3459(10)
2.008(4)
Os-C(37)
Os-C(38)
Os-C(39)
Os-C(40)
2.204(4)
2.222(4)
2.278(4)
2.283(4)
H(C5H5) exchange while, under the same conditions, the
silyl species OsH(η5-C5H5)R(SiPh3)(PiPr3) undergo SiPh3-
(Os)/H(C5H5) exchange. The resulting dihydride-alkyl
compounds are unstable toward the reductive elimina-
tion of alkane. As a result, the metallic center of the
unsaturated intermediate that forms, OsH(η5-C5H4-
SiPh3)(PiPr3), is capable of a C-H activation reaction
on one of the phenyl groups of the SiPh3 fragment, to
Os-P
Os-C(1)
Os-C(36)
2.240(4)
C(1)-C(2)
1.214(4)
C(2)-C(3)
1.424(5)
Ge-Os-P
115.97(3)
115.35(14)
79.06(9)
59.1(13)
126.65(13)
P-Os-C(1)
83.59(10)
76.7(15)
119.7(2)
120.0(5)
117.1(13)
Ge-Os-Ma
Ge-Os-C(1)
Ge-Os-H(01)
P-Os-M
P-Os-H(01)
M-Os-C(1)
M-Os-H(01)
C(1)-Os-H(01)
give the dihydride cyclometalated complex OsH2{η5-
Os-C(1)-C(2)
175.4(3)
C(1)-C(2)-C(3)
171.1(4)
a
C5H4Si(C6H4)Ph2}(PiPr3).
M is the centroid of the C(36)-C(40) Cp ligand.
We have now prepared the hydride-alkynyl com-
pounds OsH(η5-C5H5)(CtCPh)(EPh3)(PiPr3) (E ) Si,
Ge), which, in contrast to the previously mentioned
hydride-alkyl species, are stable. The high stability of
these compounds prompted us to investigate the influ-
ence of E in their deprotonation reactions. In this paper,
we report the synthesis and X-ray structure of the new
hydride-alkynyl complexes, their transformation into
vinylidenes, and the conversion of the latter species to
carbyne or allyl derivatives.
Resu lts a n d Discu ssion
1. Syn th esis a n d Ch a r a cter iza tion of OsH(η5-
C5H5)(CtCP h )(EP h 3)(P iP r 3) (E ) Si, Ge). Treatment
of tetrahydrofuran solutions of OsH(η5-C5H5)Cl(EPh3)(Pi-
Pr3) (E ) Si (1), Ge (2)) with lithium phenylacetylide
produces the replacement of the chlorine ligand by the
alkynyl group to give the hydride-alkynyl derivatives
OsH(η5-C5H5)(CtCPh)(EPh3)(PiPr3) (E ) Si (3), Ge(4)),
which are isolated as brown solids in about 60% yield
(eq 1).
(4) Dean, W. K.; Graham, W. A. G. Inorg. Chem. 1977, 16, 1061.
(5) (a) Merrifield, J . H.; Gladysz, J . A. Organometallics 1983, 2, 782.
(b) Heah, P. C.; Gladysz, J . A. J . Am. Chem. Soc. 1984, 106, 7636. (c)
Pasman, P.; Snel, J . J . M. J . Organomet. Chem. 1986, 301, 329. (d)
Heah, P. C.; Patton, A. T.; Gladysz, J . A. J . Am. Chem. Soc. 1986, 108,
1185. (e) Crocco, G. L.; Young, C. S.; Lee, K. E.; Gladysz, J . A.
Organometallics 1988, 7, 2158. (f) Crocco, G. L.; Gladysz, J . A. J . Am.
Chem. Soc. 1988, 110, 6110. (g) Milletti, M. C.; Fenske, R. F.
Organometallics 1989, 8, 420.
(6) (a) Davis, S. G.; Felkin, H.; Watts, O. J . Chem. Soc., Chem.
Commun. 1980, 159. (b) Berryhil, S. R.; Sharenow, B. J . Organomet.
Chem. 1981, 221, 143. (c) Thum, G.; Ries, W.; Greissinger, D.; Malisch,
W. J . Organomet. Chem. 1983, 252, C67. (d) Berryhill, S. R.; Clevenger,
G. L.; Burdurlu, F. Y. Organometallics 1985, 4, 1509. (e) Abbott, S.;
Baird, G. J .; Davis, S. G.; Dordor-Hedgecock, I. M.; Maberly, T. R.;
Walker, J . C.; Warner, P. J . Organomet. Chem. 1985, 289, C13. (f)
Akita, M.; Kondoh, A. J . Organomet. Chem. 1986, 299, 369. (g) Pannell,
K. H.; Vicenti, S. P.; Scott, R. C., III. Organometallics 1987, 6, 1593.
(h) Nakazawa, H.; Sone, M.; Miyoshi, K. Organometallics 1989, 8, 1564.
(i) Sharma, S.; Cervantes, J .; Mata-Mata, J . L.; Brun, M.-C.; Cervantes-
Lee, F.; Pannell, K. H. Organometallics 1995, 14, 4269. (j) Liu, L.-K.;
Chang, K.-Y.; Wen, Y.-S. J . Chem. Soc., Dalton Trans. 1998, 741. (k)
Kubo, K.; Nakazawa, H.; Kawamura, K.; Mizuta, T.; Miyoshi, K. J .
Am. Chem. Soc. 1998, 120, 6715.
Complexes 3 and 4 were characterized by MS, el-
1
emental analysis, and IR and H, 13C{1H}, and 31P{1H}
(7) Nakazawa, H.; Kawamura, K.; Kubo, K.; Miyoshi, K. Organo-
metallics 1999, 18, 4518.
(8) Atwood, J . D. Inorganic and Organometallic Reaction Mecha-
nisms; VCH: New York, 1997; Chapter 3.
(9) Baya, M.; Crochet, P.; Esteruelas, M. A.; Gutie´rrez-Puebla, E.;
Ruiz, N. Organometallics 1999, 18, 5034.
(10) Baya, M.; Crochet, P.; Esteruelas, M. A.; On˜ate, E. Organome-
tallics 2001, 20, 240.
NMR spectroscopy. Furthermore, complex 4 was char-
acterized by X-ray diffraction analysis. A view of its
molecular geometry is shown in Figure 1. Selected bond
distances and angles are listed in Table 1.
The distribution of ligands about the osmium atom
can be described as a piano-stool geometry, with the

Deprotonation of OsH(η5-C5H5)(CtCPh)(EPh3)(PiPr3)
Organometallics, Vol. 20, No. 23, 2001 4877
cyclopentadienyl ligand occupying the three-membered
face, while the four monodentate ligands lie in the four-
membered face.
instead of silyl, have been isolated and characterized.14c,15
As far as we know, complexes 3 and 4 are the first
derivatives of this class in osmium chemistry.
2. Rea ction s of OsH(η5-C5H5)(CtCP h )(SiP h 3)-
(P iP r 3). Treatment of a solution of 3 in tetrahydrofuran
with 3.0 equiv of n-butyllithium over 5 h leads to a solu-
tion which reacts with methanol to give the hydride-
vinylidene complex OsH(η5-C5H4SiPh3){dCdC(H)Ph-
}(PiPr3) (5). This compound, containing a substituted
cyclopentadienyl ligand, was isolated as a pale yellow
solid in 75% yield (eq 2).
The most noticeable feature of the structure is the
transoid positions of the bulky ligands triisopropylphos-
phine and triphenylgermyl. The angle Ge-Os-P is
115.97(3)°,whereas theC(1)-Os-H(01)angleis 117.1(13)°.
The Os-Ge bond length (2.5033(4) Å) is about 0.06 Å
shorter than that found in OsH{Ge(p-tolyl)3}(CO)2-
(PPh3)2 (2.5600(3) Å).11 This could be related to the
different oxidation states of the metallic centers, IV in
4 and II in the above-mentioned carbonyl derivative.
The environment of the germanium atom is tetrahedral,
with angles between 102.26(15) and 119.50(10)°.
The Os-C(1) distance of 2.008(4) Å is consistent with
a single bond from Os(IV) to a C(sp) atom and indicates
a low degree of metal-to-ligand back-bonding.12 The
C(1)-C(2) bond length and the Os-C(1)-C(2) and
C(1)-C(2)-C(3) angles are 1.424(5) Å and 175.4(3) and
171.1(4)°, respectively. Similar values have been found
in the cationic complex [OsH(η5-C5H5)(CtCPh)(PiPr3)2]-
PF6 for the related parameters.13
In agreement with the presence of the substituted
cyclopentadienyl ligand, the resonances of the C5H4
1
protons in the H NMR spectrum appear as an ABCD
spin system, between 5.36 and 4.99 ppm. The dCH
proton of the vinylidene displays at 2.50 ppm a double
doublet by spin coupling with the hydride (2.4 Hz) and
the phosphorus of the phosphine (2.4 Hz). The spin
coupling with the hydride ligand was confirmed by a
1H COSY spectrum. The hydride ligand gives rise to a
double doublet with a H-P coupling constant of 29.1
Hz at -14.15 ppm. In the 13C{1H} NMR spectrum the
resonances due to the CR and Câ of the vinylidene appear
at 290.8 and 111.7 ppm, respectively. The first of them
is observed as a doublet with a C-P coupling constant
of 12.8 Hz, while the second one is a singlet. The 31P-
{1H} NMR spectrum shows at 41.8 ppm a singlet, which
is split into a doublet by spin coupling with the hydride.
Under the same conditions as those previously men-
tioned for the formation of 5, the perdeuterated cyclo-
pentadienyl complex OsH(η5-C5D5)(CtCPh)(SiPh3)-
(PiPr3) (3-d5) affords OsH(η5-C5D4SiPh3){dCdC(H)Ph}(Pi-
Pr3) (5-d 4), according to eq 3.
In agreement with the presence of an alkynyl ligand
in 3, its IR spectrum in Nujol shows a band at 2093
cm-1, corresponding to the ν(CtC) vibration. The pres-
1
ence of the hydride ligand is supported by the H NMR
spectrum in benzene-d6, which contains a doublet at
-13.35 ppm with a H-P coupling constant of 32.1 Hz.
In the 13C{1H} NMR spectrum the resonances corre-
sponding to the CR and Câ atoms of the alkynyl group
appear at 78.4 and 111.9 ppm, respectively. The first of
them is observed as a doublet with a C-P coupling
constant of 21.8 Hz, while the second one is a singlet.
The 31P{1H} NMR spectrum shows a singlet at 18.1
ppm, which under off-resonance conditions is split into
a doublet as a consequence of the spin coupling with
the hydride.
The spectroscopic data of 4 agree well with those of 3
and are consistent with the structure shown in Figure
1. In the IR spectrum, the ν(CtC) band is observed at
1
2081 cm-1. The H NMR spectrum shows the hydride
resonance as a doublet at -13.42 ppm, with a H-P
coupling constant of 34.2 Hz. In the 13C{1H} NMR
spectrum, the resonances corresponding to the C(sp)
atoms appear at 75.0 (CR) and 112.6 (Câ) ppm, as a
doublet with a C-P coupling constant of 22.6 Hz and a
singlet, respectively. The 31P{1H} NMR spectrum con-
tains a singlet at 20.2 ppm, which is split into a doublet
under off-resonance conditions.
Species containing simultaneously hydride, alkynyl,
and silyl ligands have shown to be key intermediates
in the formation of cis-alkenylsilanes and alkynylsi-
lanes, by hydrosilylation and dehydrogenative silylation
of terminal alkynes.14 However, only a few compounds
of this type, or related complexes with stannyl or germyl
The presence of hydrogen atoms at the metallic center
and the Câ atom of the vinylidene of 5-d 4 is supported
1
2
by the H and H NMR spectra of this compound. The
1H NMR spectrum contains hydride and dCH reso-
nances at -14.50 and 2.51 ppm, respectively, while the
2H NMR spectrum only shows a broad resonance at 5.00
ppm, corresponding to the C5D4SiPh3 group.
(11) Clark, G. R.; Flower, K. R.; Rickard, C. E. F.; Roper, W. R.;
Salter, D. M.; Wright, L. J . J . Organomet. Chem. 1993, 462, 331.
(12) Nast, R. Coord. Chem. Rev. 1982, 47, 89.
(13) Baya, M.; Crochet, P.; Esteruelas, M. A.; Gutie´rrez-Puebla, E.;
Lo´pez, A. M.; Modrego, J .; On˜ate, E.; Vela, N. Organometallics 2000,
19, 2585.
(14) (a) Esteruelas, M. A.; Oliva´n, M.; Oro, L. A.; Tolosa, J . I. J .
Organomet. Chem. 1995, 487, 143. (b) Esteruelas, M. A.; Lo´pez, A. M.;
Oro, L. A.; Tolosa, J . I. J . Mol. Catal. A: Chem. 1995, 96, 21. (c)
Esteruelas, M. A.; Oliva´n, M.; Oro, L. A. Organometallics 1996, 15,
814.
The formation of 5 and 5-d 4 can be rationalized
according to Scheme 1. Although complexes 3 and 3-d 5
could undergo deprotonation at the metallic center and
at the cyclopentadienyl group, by action of BuLi, the
deprotonation selectively occurs at the cyclopentadienyl
n
(15) (a) Esteruelas, M. A.; Lahoz, F. J .; Oliva´n, M.; On˜ate, E.; Oro,
L. A. Organometallics 1995, 14, 3486. (b) Esteruelas, M. A.; Oro, L. A.
Coord. Chem. Rev. 1999, 193-195, 557.

4878 Organometallics, Vol. 20, No. 23, 2001
Baya et al.
Sch em e 1
Sch em e 2
as a result of the migratory insertion of the vinylidene
group into the M-H bond. As far as we know, complex
5 is the first half-sandwich hydride-vinylidene com-
pound with a metal of group 8.
The stability of the vinylidene in this type of half-
sandwich complexes depends on its substituents. The
addition of methyl iodide to the solution resulting from
the treatment of 3 with n-butyllithium does not give the
corresponding hydride-methyl-phenylvinylidene, as
ligand. The resulting species evolve by migration of the
silyl group from the osmium to the cyclopentadienyl
ligand, to afford the anion [OsH(η5-C5X4SiPh3)(CtCPh)-
(PiPr3)]-. Then, the acidic proton of methanol attacks
the Câ atom of the alkynyl group of this anionic species,
to give 5 and 5-d 4. The formation of the vinylidene
ligand agrees well with the known high nucleophility
of the Câ atom of the alkynyl groups in late-transition-
metal alkynyl complexes.16
In agreement with Scheme 1, we have also observed
that the addition of methanol-d4 to the solution resulting
from the treatment of 3 with nBuLi leads to OsH(η5-
C5H4SiPh3){dCdC(D)Ph}(PiPr3) (5-d ), according to
eq 4.
one should expect, but the metalated derivative OsH-
(η5-C5H4SiPh3){o-C6H4C(CH3)dCH}(PiPr3) (6), which
was isolated as a white solid in 60% yield (eq 5).
The formation of 6 can be rationalized according to
Scheme 2. The anion [OsH(η5-C5H4SiPh3)(CtCPh)(Pi-
Pr3)]-, generated from the reaction of 3 with n-butyl-
lithium, reacts with methyl iodide to give initially the
expected hydride-vinylidene OsH(η5-C5H4SiPh3){dCd
C(CH3)Ph}(PiPr3), in a manner similar to the formation
of 5. The presence of a methyl group at the Câ atom of
the vinylidene increases the electrophilic character of
the CR atom, favoring the migratory insertion of the
vinylidene into the Os-H bond. The insertion generates
the unsaturated five-coordinate alkenyl intermediate
Os(η5-C5H4SiPh3){CHdC(CH3)Ph}(PiPr3), which evolves
The presence of a deuterium atom at the Câ atom of
the vinylidene ligand of 5-d is strongly supported by the
2H NMR spectrum of this compound, which shows a
singlet at 2.52 ppm. In accordance with the 2H NMR
spectrum, the H NMR spectrum does not contain any
dCH resonance corresponding to the vinylidene.
Hydride-vinylidene complexes are considered impor-
tant intermediates in several homogeneous and hetero-
geneous catalytic reactions, including alkene oligomer-
ization, polymerization, methatesis of olefins,17 and
Fischer-Tropsch synthesis.18 However only a few com-
plexes of this type have been isolated.19 For metals of
group 8, with the exception of those containing chelate
ligands, the six-coordinate hydride-vinylidene com-
plexes appear to be unstable and in solution evolve to
the corresponding five-coordinate alkenyl derivatives,
1
(19) (a) Van Asselt, A.; Burger, B. J .; Gibson, V. C.; Bercaw, J . E. J .
Am. Chem. Soc. 1986, 108, 5347. (b) Ho¨rn, A.; Werner, H. Angew.
Chem., Int. Ed. Engl. 1986, 25, 737. (c) Barbaro, P.; Bianchini, C.;
Peruzzini, M.; Polo, A.; Zanobini, F.; Frediani, P. Inorg. Chim. Acta
1994, 220, 5. (d) Esteruelas, M. A.; Oro, L. A.; Ruiz, N. Organometallics
1994, 13, 1507. (e) Esteruelas, M. A.; Oro, L. A.; Valero, C. Organo-
metallics 1995, 14, 3596. (f) Guari, Y.; Sabo-Etienne, S.; Chaudret, B.
Organometallics 1996, 15, 3471. (g) Bourgault, M.; Castillo, A.;
Esteruelas, M. A.; On˜ate, E.; Ruiz, N. Organometallics 1997, 16, 636.
(h) Oliva´n, M.; Eisenstein, O.; Caulton, K. G. Organometallics 1997,
16, 2227. (i) Oliva´n, M.; Clot, E.; Eisenstein, O.; Caulton, K. G.
Organometallics 1998, 17, 897. (j) Crochet, P.; Esteruelas, M. A.; Lo´pez,
A. M.; Mart´ınez, M.-P.; Oliva´n, M.; On˜ate, E.; Ruiz, N. Organometallics
1998, 17, 4500. (k) Buil, M. L.; Esteruelas, M. A. Organometallics 1999,
18, 1798. (l) Esteruelas, M. A.; Oliva´n, M.; On˜ate, E.; Ruiz, N.; Tajada,
M. A. Organometallics 1999, 18, 2953. (m) Buil, M. L.; Eisenstein, O.;
Esteruelas, M. A.; Garc´ıa-Yebra, C.; Gutie´rrez-Puebla, E.; Oliva´n, M.;
On˜ate, E.; Ruiz, N.; Tajada, M. A. Organometallics 1999, 18, 4949.
(16) Bruce, M. I. Chem. Rev. 1991, 91, 197.
(17) (a) Turner, H. W.; Schrock, R. R.; Fellman, J . D.; Holmes, S. J .
J . Am. Chem. Soc. 1983, 105, 4942. (b) Green, J . C.; Green, M. L. H.;
Morley, C. P. Organometallics 1985, 4, 1302. (c) Beckhaus, R. Angew.
Chem., Int. Ed. Engl. 1997, 36, 686.
(18) (a) McCandlish, L. E. J . Catal. 1983, 83, 362. (b) Erley, W.;
McBreen, P. H.; Ibach, H. J . Catal. 1983, 84, 229. (c) Hoel, E. L.; Ansell,
G. B.; Leta, S. Organometallics 1986, 5, 585.

Deprotonation of OsH(η5-C5H5)(CtCPh)(EPh3)(PiPr3)
Organometallics, Vol. 20, No. 23, 2001 4879
(C(30)), -0.011(5) (C(31)), and 0.034(5) (C(32)). The
distances Os-C(25) (2.084(5) Å) and Os-C(32) (2.082(5)
Å) are statistically identical and typical for C-(sp2)
single bonds.21 The C(32)-C(31) bond length (1.346(7)
Å) is similar to those found in other alkenyl complexes22
and agrees well with the average carbon-carbon double-
bond distances (1.32(1) Å).23 The angles around C(31)
and C(32) are between 113.2(5) and 124.6(6)°, which
indicate an sp2 hybridization for these atoms.
In agreement with the presence of the hydride ligand
disposed cisoid to the phosphine, the 1H NMR spectrum
of 6 shows at -13.93 ppm a doublet with a H-P
coupling constant of 44.7 Hz. In the 13C{1H} NMR
spectrum, the resonances corresponding to the C(25)
and C(32) atoms appear at 160.9 and 130.5 ppm,
respectively, as doublets with C-P coupling constants
of 2.4 and 20.0 Hz. The 31P{1H} NMR spectrum contains
at 22.0 ppm a singlet, which under off-resonance condi-
tions is split into a doublet.
3. P r oton a tion of 5 a n d 6. Theoretical studies on
vinylidene transition-metal complexes have identified
the electron density on the Câ atom.24 In agreement with
this, the addition of 1.0 equiv of HBF4‚OEt2 to diethyl
ether solutions of 5 affords the hydride-carbyne deriva-
tive [OsH(η5-C5H4SiPh3)(tCCH2Ph)(PiPr3)]BF4 (7), as
a result of the protonation of the Câ atom of the
vinylidene ligand of 5 (eq 6). Transition-metal hydride-
F igu r e 2. Molecular diagram of the complex OsH(η5-C5H4-
SiPh3){o-C6H4C(CH3)dCH}(PiPr3) (6).
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for th e Com p lex
OsH(η5-C5H4SiP h 3){o-C6H4C(CH3)dCH}(P iP r 3) (6)
Os-P
2.3136(14)
2.270(5)
2.217(4)
2.245(5)
Os-C(4)
Os-C(5)
Os-C(25)
Os-C(32)
2.279(5)
2.292(5)
2.084(5)
2.082(5)
Os-C(1)
Os-C(2)
Os-C(3)
Si-C(1)
C(25)-C(30)
C(30)-C(31)
1.863(5)
1.419(6)
1.441(7)
C(31)-C(32)
C(31)-C(33)
1.346(7)
1.518(6)
carbyne complexes are rare,25 and as far as we know,
half-sandwich osmium complexes have not been previ-
ously reported.
P-Os-Ma
130.76(16) M-Os-C(32)
107.35(13) M-Os-H(01)
82.42(16) C(25)-Os-C(32)
69.0(13) C(25)-Os-H(01)
117.6(2)
113.4(8)
74.3(2)
74.9(13)
128.6(13)
P-Os-C(25)
P-Os-C(32)
P-Os-H(01)
M-Os-C(25)
Complex 7 was isolated as a brown solid in 87% yield.
The presence of a hydride ligand in this compound is
supported by its 1H NMR spectrum, which shows at
-12.00 ppm a doublet with a H-P coupling constant of
24.3 Hz. In addition, we should mention a singlet at 2.39
ppm, due to the CH2 group of the carbyne ligand. In
the 13C{1H} NMR spectrum, the most noticeable reso-
nance is that corresponding to the OstC carbon atom,
which is observed at 290.6 ppm, as a doublet with a C-P
coupling constant of 15.1 Hz. The 31P{1H} NMR spec-
trum contains at 47.2 ppm a singlet, which under off-
resonance conditions is split into a doublet.
121.0(2)
C(32)-Os-H(01)
Os-C(25)-C(30)
Os-C(32)-C(31)
C(25)-C(30)-C(31) 112.4(5)
118.6(4)
121.3(5)
C(30)-C(31)-C(32) 113.2(5)
C(30)-C(31)-C(33) 122.0(5)
C(32)-C(31)-C(33) 124.6(6)
a
M is the centroid of the C(1)-C(5) Cp ligand.
by C-H activation of an ortho CH-aryl bond into 6.
The activation of the phenyl instead of the methyl group
of the alkenyl ligand agrees well with the kinetic and
thermodynamic preference of the aromatic C-H activa-
tion.20
(21) Esteruelas, M. A.; Gutie´rrez-Puebla, E.; Lo´pez, A. M.; On˜ate,
E.; Tolosa, J . I. Organometallics 2000, 19, 275 and references therein.
(22) See for example: (a) Werner, H.; Esteruelas, M. A.; Otto, H.
Organometallics 1986, 5, 2295. (b) Werner, H.; Weinand, R.; Otto, H.
J . Organomet. Chem. 1986, 307, 49. (c) Espuelas, J .; Esteruelas, M.
A.; Lahoz, F. J .; Oro, L. A.; Valero, C. Organometallics 1993, 12, 663.
(d) Buil, M. L.; Esteruelas, M. A.; Lo´pez, A. M.; On˜ate, E. Organome-
tallics 1997, 16, 3169. (e) Bohanna, C.; Callejas, B.; Edwards, A. J .;
Esteruelas, M. A.; Lahoz, F. J .; Oro, L. A.; Ruiz, N.; Valero, C.
Organometallics 1998, 17, 373.
A view of the molecular geometry of 6 is shown in
Figure 2. Selected bond distances and angles are listed
in Table 2. The distribution of ligands around the
osmium atom can be described as a four-legged piano-
stool geometry with the metalated carbon atom C(25)
transoid to the phosphine and cisoid to the hydride
ligand. The P-Os-C(25) and C(25)-Os-H(01) angles
are 107.35(13) and 74.9(13)°, respectively.
The orthometalated alkenyl ligand acts with a bite
angle of 74.3(2)°. The five-membered heterometallacycle
is almost planar. The deviations (in Å) from the best
plane are -0.0001(3) (Os), 0.034(5) (C(25)), -0.028(5)
(23) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
D. G.; Taylor, R. J . Chem. Soc., Dalton Trans. 1989, S1.
(24) Kostic, N. M.; Fenske, R. F. Organometallics 1982, 1, 974.
(25) (a) Leeaphon, M.; Fanwick, P. E.; Walton, R. A. J . Am. Chem.
Soc. 1992, 114, 1890. (b) Espuelas, J .; Esteruelas, M. A.; Lahoz, F. J .;
Oro, L. A.; Ruiz, N. J . Am. Chem. Soc. 1993, 115, 4683. (c) Spivak, G.
J .; Coalter, J . N.; Oliva´n, M.; Eisenstein, O.; Caulton, K. G. Organo-
metallics 1998, 17, 999. (d) Werner, H.; J ung, S.; Weberndo¨rfer, B.;
Wolf, J . Eur. J . Inorg. Chem. 1999, 951.
(20) J ones, W. D.; Feher, F. J . Acc. Chem. Res. 1989, 22, 91.

4880 Organometallics, Vol. 20, No. 23, 2001
Baya et al.
Sch em e 3
The addition of 1.0 equiv of HBF4‚OEt2 to diethyl
ether solutions of 6 initially gives the hydride-carbyne
derivative [OsH(η5-C5H4SiPh3){tCCH(CH3)Ph}(PiPr3)]-
BF4 (8). The formation of this complex according to eq
7 proves that in fact, as is shown in Scheme 2, in
solution complex 6 is in equilibrium with no detectable
concentrations of the hydride-vinylidene OsH(η5-C5H4-
SiPh3){dCdC(CH3)Ph}(PiPr3).
ligand is supported by the 2H NMR spectrum of 8-d ,
which contains a broad singlet at 2.58 ppm, as only one
resonance. Similarly to 8, in solution, 8-d evolves into
[OsH(η5-C5H4SiPh3){η3-CH2C(C6H4D)CH2}(PiPr3)]BF4
(9-d ), containing the deuterium atom at one of the ortho
carbon atoms of the phenyl group of the allyl ligand.
Its position is strongly supported by the 2H NMR
spectrum of 9-d , which contains, as only one resonance,
a singlet at 7.35 ppm.
The previously mentioned observations suggest that,
although the protonation of the hydride-vinylidene is
kinetically favored, it is reversible and that the proto-
nation on 6 occurs at the metalated carbon atom of the
aryl group (Scheme 3). Thus, once the unsaturated
hydride-alkenyl [OsH(η5-C5H4SiPh3){CHdC(CH3)Ph}(Pi-
Pr3)]BF4 is formed, the reductive elimination of the
olefin affords [Os(η5-C5H4SiPh3){η2-CH2dC(CH3)Ph}-
(PiPr3)]BF4, which evolves by C-H activation of the
methyl group of the alkene into 9 or 9-d . The reductive
elimination in [OsH(η5-C5H4SiPh3){CHdC(CH3)Ph}(Pi-
Pr3)]BF4 is probably favored by its unsaturated char-
acter,26 whereas the higher stability of a M(η3-allyl)
bond with regard to an M-aryl bond appears to be the
driving force for the activation of the methyl instead the
phenyl group, in the intermediate [Os(η5-C5H4SiPh3)-
{η2-CH2dC(CH3)Ph}(PiPr3)]BF4.27
Figure 3 shows a view of the molecular geometry of
9. Selected bond distances and angles are listed in Table
3. The distribution of ligands around the osmium atom
can be described as a four-legged piano-stool geometry,
where the allyl ligand occupies two cisoid positions with
a bite angle of 64.2(2)°. The atoms C(24), C(25), C(26),
and C(27) of the allyl ligand are coplanar (maximum
deviation 0.017(5) Å for C(25)) and form a dihedral angle
of 28.04(18)° with the cyclopentadienyl ring. As a result
of the disposition of the allyl ligand, the separation
between the central carbon atom, C(25), and the metal
(2.184(4) Å) is shorter than the separation between the
metal and the terminal carbon atoms C(24) (2.217(4)
Å) and C(26) (2.196(4) Å). The carbon-carbon distances
As a result of the chirality of the metallic center and
the Câ atom of the carbyne ligand, complex 8 was
isolated as a 1:1 mixture of the racemic forms of two
diastereoisomers. In the 1H NMR spectrum of the
mixture, the most noticeable resonances are those
corresponding to the hydride ligands, which appear at
-11.60 and -11.68 ppm as doublets with H-P coupling
constants of about 25 Hz. In the 13C{1H} NMR spectrum
the OsCR atoms display doublets at 294.2 and 294.9
ppm, with C-P coupling constants of about 8 Hz. The
31P{1H} NMR spectrum contains two singlets at 47.9
and 47.8 ppm.
In solution, complex 8 evolves into the hydride-allyl
isomer [OsH(η5-C5H4SiPh3){η3-CH2C(Ph)CH2}(PiPr3)]-
BF4 (9). At 45 °C, the conversion shown in eq 8 is
quantitative after 96 h. This indicates that 8 is the
product of kinetic control in the protonation of 6,
whereas 9 is the product of thermodynamic control.
The protonation of 6 with DBF4 affords [OsH(η5-C5H4-
SiPh3){tCCD(CH3)Ph}(PiPr3)]BF4 (8-d ). The presence
of the deuterium atom at the Câ atom of the carbyne
(26) Crabtree, R. H. The Organometallic Chemistry of the Transition
Metals; Wiley: New York, 1988.
(27) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Sola, E.
J . Am. Chem. Soc. 1996, 118, 89.

Deprotonation of OsH(η5-C5H5)(CtCPh)(EPh3)(PiPr3)
Organometallics, Vol. 20, No. 23, 2001 4881
4. The treatment of 4 in tetrahydrofuran with 3.0 equiv
of n-butyllithium and the subsequent addition of metha-
nol to the resulting solution do not lead to a hydride-
vinylidene derivative, containing a germyl-substituted
cyclopentadienyl ligand (similar to 5), but afford the
germyl-vinylidene Os(η5-C5H5)(GePh3){dCdC(H)Ph}(Pi-
Pr3) (10), according to eq 9.
Complex 10 was isolated as a pale brown solid in 65%
yield. In the 1H NMR spectrum, the most noticeable
resonances are a singlet at 5.04 ppm, corresponding to
the intact cyclopentadienyl ligand, and a doublet at 3.14
ppm with a H-P coupling constant of 1.2 Hz, due to
the dCH proton of the vinylidene. In the 13C{1H}
spectrum, the CR resonance of the unsaturated η1-carbon
ligand appears at 299.5 ppm, as a doublet with a C-P
coupling constant of 12.0 Hz, whereas the Câ resonance
is observed at 124.2 ppm, as a singlet. The 31P{1H} NMR
spectrum contains a singlet at 19.9 ppm.
Interestingly, the addition of methanol-d4 to the
solution resulting from the treatment of 4 with n-
butyllithium gives the double-deuterated complex Os-
(η5-C5H4D)(GePh3){dCdC(D)Ph}(PiPr3) (10-d 2). The po-
sitions of the deuterium atoms at the cyclopentadienyl
and vinylidene ligands are strongly supported by the
2H NMR spectrum of the compound, which shows two
singlets at 5.01 and 3.21 ppm with a 1:1 intensity ratio.
The formation of 10-d 2 according to eq 10 indicates
that the treatment of 4 with n-butyllithium produces a
double deprotonation, at the metallic center and at the
cyclopentadienyl ligand. Furthermore, it should be noted
F igu r e 3. Molecular diagram of the complex [OsH(η5-
C5H4SiPh3){η3-CH2C(Ph)CH2}(PiPr3)]BF4 (9).
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for th e Com p lex
[OsH(η5-C5H4SiP h 3){η3-CH2C(P h )CH2}(P iP r 3)]BF 4
(9)
Os-P
2.3500(11)
2.255(4)
2.266(4)
2.266(4)
2.246(4)
Os-C(5)
2.188(4)
2.217(4)
2.184(4)
2.196(4)
Os-C(1)
Os-C(2)
Os-C(3)
Os-C(4)
Os-C(24)
Os-C(25)
Os-C(26)
Si-C(1)
C(24)-C(25)
1.869(4)
1.411(6)
C(25)-C(26)
C(25)-C(27)
1.415(6)
1.483(6)
P-Os-Ma
122.89(16) M-Os-H(01)
100.97(15) C(24)-Os-C(25)
112.59(12) C(24)-Os-C(26)
83.85(13) C(24)-Os-H(01)
108.6(16)
37.39(17)
64.2 (2)
75.3(19)
37.70(16)
112.7(19)
126.2(19)
P-Os-C(24)
P-Os-C(25)
P-Os-C(26)
P-Os-H(01)
M-Os-C(24)
M-Os-C(25)
M-Os-C(26)
70.3(17)
135.1(2)
C(25)-Os-C(26)
C(25)-Os-H(01)
118.84(18) C(26)-Os-H(01)
125.0(2)
Os-C(24)-C(25)
Os-C(25)-C(24)
Os-C(25)-C(26)
70.1(2)
72.6(2)
71.6(2)
Os-C(26)-C(25)
70.7(2)
C(24)-C(25)-C(26) 112.2(4)
C(24)-C(25)-C(27) 124.2(4)
C(26)-C(25)-C(27) 123.6(4)
Os-C(25)-C(27) 120.8(3)
a
M is the centroid of the C(1)-C(5) Cp ligand.
that, in contrast to the silyl complex 3, the deprotona-
tion of the cyclopentadienyl ligand of 4 does not give
way to the migration of the germyl group from the
osmium atom to the cyclopentadienyl ligand. This
agrees well with the previously determined higher
thermodynamic stability of the Os-Ge bond in com-
parison with the Os-Si bond.9
within the allylic moiety are 1.411(6) Å for C(24)-C(25)
and 1.415(6) Å for C(25)-C(26). Both bond lengths are
about 0.07 Å shorter than the C(25)-C(27) distance
(1.483(6) Å), which corresponds to a carbon-carbon
single bond. The angle C(24)-C(25)-C(26) is 112.2(4)°.
In agreement with the structure shown in Figure 3,
the 1H NMR spectrum shows four resonances for the
allylic protons at 4.46, 3.77, 2.15, and 1.82 ppm. In the
high-field region the hydride displays a doublet at
-13.37 ppm, with a H-P coupling constant of 30.0 Hz.
In the 13C{1H} NMR spectrum, the resonances corre-
sponding to the allyl carbon atoms are observed at 86.2
(C(25)), 28.4 (C(24)), and 18.7 (C(26)) ppm. The 31P{1H}
NMR spectrum contains a singlet at 19.3 ppm, which
under off-resonance conditions is split into a doublet.
4. Rea ction s of OsH(η5-C5H5)(CtCP h )(GeP h 3)-
(P iP r 3). There are significant differences in behavior
between the silyl complex 3 and its germyl counterpart
Theoretical studies28 suggest that in these types of
compounds, in addition to the M-ER3 σ bond there is
an important π-bonding, as a result of the donation of
electron density from d orbitals of the metal to a linear
combination of E-R σ* orbitals. The higher acidity of
the hydride of 4 with regard to the hydride of 3 suggests
that the larger fortress of the Os-Ge bond is a result
of a more efficient d-π* donation to the germyl than to
the silyl group: i.e., the GePh3 group is a better π-ac-
(28) See for example: Hu¨bler, K.; Hunt, P. A.; Maddock, S. M.;
Rickard, C. E. F.; Roper, W. R.; Salter, D. M.; Schwerdtfeger, P.;
Wright, L. J . Organometallics 1997, 16, 5076.

4882 Organometallics, Vol. 20, No. 23, 2001
Baya et al.
ceptor ligand than the SiPh3 group. As a result, the
electron density at the metallic center of 4 is lower than
at the metallic center of 3. Thus, the Os-H bond is more
polarized in 4 than in 3, and therefore, the hydride of 4
is more acidic than the hydride of 3.
In agreement with the double deprotonation of 4, the
addition of methyl iodide to the solution resulting from
the treatment of 4 with n-butyllithium gives Os(η5-C5H4-
CH3)(GePh3){dCdC(CH3)Ph}(PiPr3) (11), according to
eq 11.
noticeable resonances are two doublets at about 300
ppm, with C-P coupling constants of about 8 Hz, due
to the OstC resonances. The 31P{1H} NMR spectrum
shows two singlets at 28.6 and 30.8 ppm.
In contrast to 8, in solution, complex 13 is stable and
does not evolve into an allyl species related to 9. This
indicate that the migratory insertion of the methylphe-
nylvinylidene into an Os-GePh3 bond is less favored
than the insertion into an Os-H bond, which can be
related to the lower nucleophilic power of a germyl
group with regard to a hydride ligand.
Con clu d in g Rem a r k s
This paper reveals that the group 14 element Si or
Ge has a marked influence on the deprotonation reac-
tions of the hydride-alkynyl complexes OsH(η5-C5H5)-
(CtCPh)(EPh3)(PiPr3) (E ) Si, Ge). While the deproto-
nation of the silyl derivative with n-butyllithium is
single and selectively occurs at the cyclopentadienyl
ligand, the deprotonation of the germyl compound is
double and takes place both at the cyclopentadienyl
group and at the metallic center. Furthermore, the
deprotonation of OsH(η5-C5H5)(CtCPh)(SiPh3)(PiPr3) is
accompanied by the migration of the silyl group from
the osmium atom to the cyclopentadienyl ligand.
As a consequence of these differences, depending on
the group 14 element, different types of vinylidene
derivatives are obtained from the reactions of OsH(η5-
C5H5)(CtCPh)(EPh3)(PiPr3) with n-butyllithium and
electrophiles. While the silyl complex leads to hydride-
vinylidenes containing a silyl-substituted cyclopentadi-
enyl ligand, OsH(η5-C5H4SiPh3){dCdC(X)Ph}(PiPr3),
the germyl complex gives rise to germyl-vinylidenes of
the type Os(η5-C5H4X)(GePh3){dCdC(X)Ph}(PiPr3) (X
) electrophile). Both types of vinylidene compounds
afford carbyne derivatives by protonation with HBF4.
The germyl-vinylidene complexes are stable with
regard to the migratory insertion of the vinylidene into
the Os-Ge bond. However, the stability of the hydride-
vinylidenes, with regard to the migratory insertion of
the vinylidene into the Os-H bond, depends on the
substituents of the vinylidene. Thus, in solution, the
complex OsH(η5-C5H4SiPh3){dCdC(CH3)Ph}(PiPr3) is
Complex 11 was isolated as a pale red solid in 72%
yield. The presence of the substituted cyclopentadienyl
ligand in the complex is supported by its 1H NMR
spectrum, which shows between 5.01 and 4.07 ppm an
ABCD spin system corresponding to the cyclopentadi-
enyl protons. In addition, the spectrum contains two
singlets due to the C5H4CH3 and dCCH3 methyl groups
at 2.15 and 1.95 ppm. In the 13C{1H} NMR spectrum,
the CR and Câ resonances of the vinylidene appear at
303.4 and 115.1 ppm, respectively. The first of them is
observed as a doublet with a C-P coupling constant of
12.0 Hz and the second one as a singlet. The 31P{1H}
NMR spectrum shows a singlet at 18.7 ppm.
5. P r oton a tion of 10 a n d 11. Similarly to 5, the
vinylidene ligands of 10 and 11 are capable of undergo-
ing the attack of electrophiles. Thus, the addition of 1.0
equiv of HBF4‚OEt2 to diethyl ether solutions of 10 and
11 leads to the corresponding germyl-carbyne deriva-
tives [Os(η5-C5H5)(GePh3)(tCCH2Ph)(PiPr3)]BF4 (12)
and [Os(η5-C5H4CH3)(GePh3){tCCH(CH3)Ph}(PiPr3)]-
BF4 (13), as a result of the addition of the proton of the
acid to the Câ atom of the vinylidene ligands (eq 12).
unstable and evolves into the metalated species OsH-
(η5-C5H4SiPh3){o-C6H4C(CH3)dCH}(PiPr3), which re-
sults from the migratory insertion of the methylphe-
nylvinylidene into the Os-H bond of OsH(η5-C5H4SiPh3)-
{dCdC(CH3)Ph}(PiPr3) and the subsequent C-H acti-
vation of an ortho C-H bond of the aryl group of the
alkenyl ligand, in the resulting unsaturated intermedi-
ate [Os(η5-C5H4SiPh3){CHdC(CH3)Ph}(PiPr3).
Complex 12 was isolated as a pale brown solid in 83%
yield. In the H NMR spectrum the CH2 group of the
1
carbyne ligand gives rise to an AB spin system, defined
by δA 3.04, δB 2.85 ppm, and J AB ) 18.9 Hz. In the 13C-
{1H} spectrum, the resonance corresponding to the Ost
C carbon atom is observed at 297.6 ppm, as a doublet
with a C-P coupling constant of 8.8 Hz. The 31P{1H}
NMR spectrum contains a singlet at 31.2 ppm.
The protonation of the vinylidene of OsH(η5-C5H4-
SiPh3){dCdC(CH3)Ph}(PiPr3) is kinetically favored with
regard to the protonation of the metalated aryl group
of OsH(η5-C5H4SiPh3){o-C6H4C(CH3)dCH}(PiPr3). How-
ever, the product of thermodynamic control of the
reaction is the hydride-allyl derivative [OsH(η5-C5H4-
SiPh3){η3-CH2C(Ph)CH2}(PiPr3)]+, which results from
Complex 13 was isolated as a pale yellow solid in 87%
yield. In solution, it exists as a 2:1 mixture of the
racemic forms of two diastereoisomers, as a result of
the chirality of the metallic center and the Câ atom of
1
the carbyne ligand. Thus, the H NMR spectrum shows
the protonation of the metalated aryl group of OsH(η5-
two quartets at about 3 ppm with H-H coupling
constants of about 7 Hz, corresponding to the CH proton
of the carbyne. In the 13C{1H} NMR spectrum, the most
C5H4SiPh3){o-C6H4C(CH3)dCH}(PiPr3). The formation
of this allyl complex involves the C-H activation of the

Deprotonation of OsH(η5-C5H5)(CtCPh)(EPh3)(PiPr3)
Organometallics, Vol. 20, No. 23, 2001 4883
128.6, 124.4 (+, all s, C’s of phenyl group in CPh); 127.5 (+, s,
Cpara Ph in GePh3); 112.6 (-, s, OsCtC); 82.8 (+, s, η5-C5H5);
75.0 (-, d, OsC, J CP ) 22.6 Hz); 28.9 (+, d, PCH, J CP ) 29.8
Hz); 20.3, 19.7 (+, both s, PCHCH3). 31P{1H} NMR (121.4 MHz,
C6D6, 293 K): δ 20.2 (s, d in off-resonance). MS (FAB+): m/z
822 (M+), 745 (M+ - Ph).
P r epar ation of OsH(η5-C5H4SiP h 3){dCdC(H)P h }(P iP r 3)
(5). To a cold solution (-30 °C) of OsH(η5-C5H5)(CtCPh)-
(SiPh3)(PiPr3) (201 mg, 0.26 mmol) in 15 mL of THF was added
n-butyllithium (0.30 mL, 2.6 M, 0.78 mmol), and the mixture
was left to react for 5 h, keeping the temperature at -30 °C.
Methanol (1 mL) was then added, and the solution was
vacuum-dried. The resulting residue was washed with metha-
nol (3 × 3 mL), leading to a pale yellow solid. Yield: 151 mg
methyl group of the coordinated olefin, in the interme-
diate [Os(η5-C5H4SiPh3){η2-CH2dC(CH3)Ph}(PiPr3)]+.
In conclusion, there are strong differences between
the organometallic chemistry of the complexes OsH(η5-
C5H5)(CtCPh)(SiPh3)(PiPr3) and OsH(η5-C5H5)(CtCPh)-
(GePh3)(PiPr3). These differences are a direct conse-
quence of the different natures of the group 14 elements
of the complexes.
2
1
Exp er im en ta l Section
All reactions were carried out with rigorous exclusion of air
using Schlenk-tube techniques. Solvents were dried by the
usual procedures and distilled under argon prior to use. The
starting materials OsH(η5-C5H5)Cl(SiPh3)(PiPr3) (1) and OsH-
(η5-C5H5)Cl(GePh3)(PiPr3) (2) were prepared by the published
methods.9 The starting materials OsH(η5-C5D5)Cl(SiPh3)(PiPr3)
(1-d 5) and OsH(η5-C5D5)(CtCPh)(SiPh3)(PiPr3) (3-d 5) were
prepared by using procedures similar to those for the nondeu-
terated counterparts. The precursor Os(η5-C5D5)Cl(PiPr3)2 was
prepared by the same method described for Os(η5-C5H5)Cl(Pi-
Pr3)2, but using TlC5D5.29 TlC5D5 was prepared as previously
described.30
(75%). Anal. Calcd for
C40H47OsPSi: C, 61.81; H, 6.11.
Found: C, 61.65; H, 6.34. IR (Nujol, cm-1): ν(Os-H) 2108 (w);
ν(OsdCdC) 1614 (m). 1H NMR (300 MHz, C6D6, 293 K): δ
7.90-6.80 (20 H, Ph); 5.36-4.99 (ABCD system, 4 H, signals
of η5-C5H4); 2.50 (dd, 1 H, OsdCdCH, J HP ) 2.4 Hz, J HH
)
)
4
4
3
2.4 Hz); 1.94 (m, 3 H, PCH); 0.86 (dd, 9 H, PCHCH3, J HP
3
3
14.1 Hz, J HH ) 7.2 Hz); 0.84 (dd, 9 H, PCHCH3, J HP ) 14.1
3
2
Hz, J HH ) 7.2 Hz); -14.15 (dd, 1 H, OsH, J HP ) 29.1 Hz,
4J HH ) 2.4 Hz). 13C{1H} NMR (75.5 MHz, C6D6, 293 K): δ 290.8
2
(d, OsdC, J CP ) 12.8 Hz); 137.0, 127.9 (both s, Cortho, Cmeta of
In the NMR spectra, chemical shifts are expressed in ppm
downfield from Me4Si (1H and 13C) and 85% H3PO4 (31P).
Coupling constants, J , are given in Hertz.
Ph in GePh3); 136.3 (s, Cipso of Ph in SiPh3); 135.4 (s, Cipso of
Ph in dCPh); 129.7, 127.7 (both s, Cortho and Cmeta of Ph in
dCPh); 128.1 (s, Cpara of Ph in SiPh3); 124.9 (s, Cpara of Ph in
dCPh); 111.7 (s, OsdCdC); 91.8, 88.8, 86.7, 86.1 (all s, tertiary
P r ep a r a t ion of OsH(η5-C5H5)(CtCP h )(SiP h 3)(P iP r 3)
(3). To a solution of OsH(η5-C5H5)Cl(SiPh3)(PiPr3) (326 mg, 0.46
mmol) in 10 mL of THF was added an excess of lithium
phenylacetylide (102 mg, 0.94 mmol). The mixture was stirred
for 18 h, and methanol (1 mL) was added. After 1 min of
stirring, the solution was vacuum-dried, and the resulting
sticky residue was washed with methanol (3 × 5 mL), leading
to a pale brown solid. Yield: 217 mg (61%). Anal. Calcd. for
2
C’s in η5-C5H4); 84.1 (d, quaternary C in η5-C5H4, J CP ) 6.3
1
Hz); 27.9 (d, PCH, J CP ) 30.8 Hz); 19.9, 19.7 (both s,
PCHCH3). 31P{1H} NMR (121.4 MHz, C6D6, 293 K): δ 41.8 (s,
d in off-resonance). MS (FAB+): m/z 778 (M+).
P r epar ation of OsH(η5-C5D4SiP h 3){dCdC(H)P h }(P iP r 3)
(5-d 4). To a cold solution (-30 °C) of OsH(η5-C5D5)(CtCPh)-
(SiPh3)(PiPr3) (161 mg, 0.21 mmol) in 10 mL of THF was added
n-butyllithium (0.20 mL, 2.6 M, 0.52 mmol), and the mixture
was left to react for 5 h, keeping the temperature at -30 °C.
Methanol (1 mL) was then added, and the solution was
vacuum-dried. The resulting residue was washed with metha-
nol (3 × 3 mL), leading to a pale yellow solid. Yield: 119 mg
C
40H47SiOsP: C, 61.81; H, 6.11. Found: C, 61.44; H, 6.28. IR
1
(Nujol, cm-1): ν(Os-H) 2179 (vw); ν(CtC) 2093 (s). H NMR
(300 MHz, C6D6, 293 K): δ 8.20-6.90 (20 H, Ph); 4.77 (s, 5 H,
η5-C5H5); 2.07 (m, 3 H, PCH); 0.91 (dd, 9 H, PCHCH3, J HP
)
3
3
3
13.8 Hz, J HH ) 7.2 Hz); 0.78 (dd, 9 H, PCHCH3, J HP ) 13.8
Hz, 3J HH ) 7.2 Hz); -13.35 (d, 1 H, OsH, 2J HP ) 32.1 Hz). 13C-
{1H} NMR (75.5 MHz, C6D6, 293 K, plus APT): δ 145.8 (-, s,
Cipso Ph in SiPh3); 137.2, 127.0 (+, both s, Cortho and Cmeta Ph
in SiPh3); 136.0 (-, s, Cipso Ph in CPh); 131.4, 128.2 (+, both s,
Cortho and Cmeta Ph in C-Ph); 127.7 (+, s, Cpara Ph in SiPh3);
124.3 (+, s, Cpara Ph in C-Ph); 111.9 (-, s, OsCtC); 83.3 (+,
1
(74%). H NMR (300 MHz, C6D6, 293 K): δ 8.10-6.80 (20 H,
Ph); 2.51 (br s, 1 H, OsdCdCH); 1.94 (m, 3 H, PCH); 0.88 (dd,
3
3
9 H, PCHCH3, J HP ) 14.1 Hz, J HH ) 7.2 Hz); 0.84 (dd, 9 H,
3
3
PCHCH3, J HP ) 14.1 Hz, J HH ) 7.2 Hz); -14.15 (dd, 1 H,
OsH, J HP ) 30.0 Hz, J HH ) 2.7 Hz). 2H NMR (46.1 MHz,
C6H6, 293 K): δ 5.01 (br signal, η5-C5D4). 31P{1H} NMR (121.4
MHz, C6D6, 293 K): δ 42.2 (s, d in off-resonance).
2
4
2
s, η5-C5H5); 78.4 (-, d, OsC, J CP ) 21.8 Hz); 28.9 (+, d, PCH,
1J CP ) 29.1 Hz); 20.3, 19.7 (+, both s, PCHCH3). 31P{1H} NMR
(121.4 MHz, C6D6, 293 K): δ 18.1 (s, d in off-resonance). MS
(FAB+): m/z 778 (M+).
P r epar ation of OsH(η5-C5H4-SiP h 3){dCdC(D)P h }(P iP r 3)
(5-d ). To a cold solution (-30 °C) of OsH(η5-C5H5)(CtCPh)-
(SiPh3)(PiPr3) (180 mg, 0.23 mmol) in 12 mL of THF was added
n-butyllithium (0.20 mL, 2.6 M, 0.52 mmol), and the mixture
was left to react for 5 h, keeping the temperature at -30 °C.
Methanol-d4 (1 mL) was then added, and the solution was
vacuum-dried. The resulting residue was washed with metha-
nol (3 × 3 mL), leading to a pale yellow solid. Yield: 130 mg
P r ep a r a t ion of OsH (η5-C5H 5)(CtCP h )(GeP h 3)(P iP r 3)
(4). To a solution of OsH(η5-C5H5)Cl(GePh3)(PiPr3) (427 mg,
0.56 mmol) in 20 mL of THF was added an excess of lithium
phenylacetylide (160 mg, 1.48 mmol). The mixture was stirred
for 24 h, and methanol (1 mL) was added. After 1 min of
stirring, the solution was vacuum-dried, and the resulting
sticky residue was washed with methanol (3 × 5 mL), leading
to a pale brown solid. Yield: 286 mg (62%). Anal. Calcd for
1
(72%). H NMR (300 MHz, C6D6, 293 K): δ 7.90-6.80 (20 H,
Ph); 5.36-4.99 (ABCD system, 4 H, signals of η5-C5H4); 1.94
3
3
(m, 3 H, PCH); 0.86 (dd, 9 H, PCHCH3, J HP ) 14.1 Hz, J HH
C
40H47GeOsP: C, 58.48; H, 5.77. Found: C, 58.27; H, 5.67. IR
3
3
) 7.2 Hz); 0.84 (dd, 9 H, PCHCH3, J HP ) 14.1 Hz, J HH ) 7.2
Hz); -14.15 (d, 1 H, OsH, 2J HP ) 29.1 Hz). 2H NMR (46.1 MHz,
C6H6, 293 K): δ 2.52 (s, 1 D, OsdCdCD). 31P{1H} NMR (121.4
MHz, C6D6, 293 K): δ 42.2 (s, d in off-resonance).
1
(Nujol, cm-1): ν(Os-H) 2158 (vw); ν(CtC) 2081 (s). H NMR
(300 MHz, C6D6, 293 K): δ 8.20-6.90 (20 H, Ph); 4.79 (s, 5 H,
η5-C5H5); 2.15 (m, 3 H, PCH); 0.88 (dd, 9 H, PCHCH3, J HP
)
3
3
3
14.1 Hz, J HH ) 7.2 Hz); 0.77 (dd, 9 H, PCHCH3, J HP ) 14.1
3
2
Hz, J HH ) 7.2 Hz); -13.42 (d, 1 H, Os-H, J HP ) 34.2 Hz).
13C{1H} NMR (75.5 MHz, C6D6, 293 K, plus APT): δ 147.4 (-,
s, Cipso Ph in GePh3); 137.2, 127.8 (+, both s, Cortho and Cmeta
Ph in GePh3); 136.6 (-, s, Cipso Ph in CPh); 135.8, 131.5, 129.4,
P r epar ation of OsH(η5-C5H4SiP h 3){o-C6H4C(CH3)dCH}-
(P iP r 3) (6). To a solution of OsH(η5-C5H5)(CtCPh)(SiPh3)(Pi-
Pr3) (186 mg, 0.24 mmol) in 10 mL of THF was added an excess
of n-butyllithium (0.25 mL, 2.6 M, 0.65 mmol), and the mixture
was left to react for 10 min. Methyl iodide (0.40 mL) was then
added, and the solution was vacuum-dried. The resulting
residue was washed with methanol (3 × 3 mL), leading to a
(29) Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa, J . I. Orga-
nometallics 1997, 16, 4657.
(30) Anderson, G. K.; Cross, R. J .; Phillips, I. G. J . Chem. Soc., Chem.
Commun. 1978, 709.
white solid. Yield: 112 mg (60%). Anal. Calcd for C41H49
-

4884 Organometallics, Vol. 20, No. 23, 2001
Baya et al.
OsPSi: C, 62.25; H, 6.24. Found: C, 61.90; H, 6.45. IR (Nujol,
cm-1): ν(Os-H) 2149 (s). 1H NMR (300 MHz, C6D6, 293 K): δ
8.00-6.80 (20 H, signals corresponding to CH’s of aryl groups
and OsCHd); 5.17-4.90 (ABCD system, 4 H, signals of η5-
C5H4); 2.25 (s, 3 H, dCCH3); 1.98 (m, 3 H, PCH); 0.74 (dd, 9
H, PCHCH3, J HP ) 13.8 Hz, J HH ) 7.2 Hz); 0.61 (dd, 9 H,
PCHCH3, 3J HP ) 13.8 Hz, 3J HH ) 7.2 Hz); -13.93 (d, 1 H, OsH,
2J HP ) 44.7 Hz). 13C{1H} NMR (75.5 MHz, C6D6, 293 K, plus
APT): δ 160.9 (-, d, CR in OsC6H4, 2J CP ) 2.4 Hz); 151.9, 149.8
of Ph groups); 6.60-4.66 (ABCD system, 4 H, signals of η5-
C5H4); 2.61 (q, 1 H, tCCH, 3J HH ) 6.9 Hz); 1.84 (m, 3 H, PCH);
1.30-0.80 (21H, signals of PCHCH3 and CH(Ph)CH3); -11.68
(d, 1 H, OsH, 2J HP ) 24.9 Hz). 13C{1H} NMR (75.5 MHz, CDCl3,
2
293 K): δ 294.9 (d, OstC, J CP ) 7.6 Hz); 137.0-127.0 (all s,
3
3
C signals of Ph groups); 104.9, 92.9, 92.0, 88.6 (all s, tertiary
2
C’s in η5-C5H4); 90.1 (d, quaternary C in η5-C5H4SiPh3, J CP
)
1
4.3 Hz); 61.9 (s, tCCH); 30.5 (d, PCH, J CP ) 31.9 Hz); 20.0-
19.0 (all s, signals of PCHCH3); 18.1 (s, CH(Ph)CH3). 31P{1H}
NMR (121.4 MHz, CDCl3, 293 K): δ 47.8 (s). MS (FAB+): m/z
793 (M+).
(-, both d, the other two quaternary C’s in Os{o-C6H4C(CH3)d
P r ep a r a tion of [OsH(η5-C5H4SiP h 3){η3-CH2C(P h )CH2}-
(P iP r 3)]BF 4 (9). A solution of [OsH(η5-C5H4SiPh3){tC-CH-
(CH3)Ph}(PiPr3)]BF4 (72 mg, 0.082 mmol) in 8 mL of dichlo-
romethane was heated to 45 °C for 96 h. Afterward, the
mixture was vacuum-dried and washed with diethyl ether (4
× 5 mL), leading to a white solid. Yield: 65 mg (91%). Anal.
Calcd for C41H50BF4OsPSi: C, 56.02; H, 5.73. Found: C, 56.05;
H, 5.58. IR (Nujol, cm-1): ν(Os-H) 2189 (vw); ν(BF4) 1054 (s).
1H NMR (300 MHz, CDCl3, 293 K): δ 7.60-7.10 (20 H, signals
of Ph groups); 6.76-3.26 (ABCD system, 4 H, signals of η5-
C5H4); 4.46, 3.77 (both dd, 1 H each, two protons of the allyl
CH}, 3J CP ) 3.9, 3.8 Hz respectively); 147.0, 122.9, 122.3, 122.1
(+, all s, tertiary C’s in C6H4); 137.3, 128.3 (+, both s, Cortho
and Cmeta of Ph in SiPh3); 135.0 (-, s, Cipso of Ph in SiPh3);
2
130.5 (+, d, OsCHdC(CH3), J CP ) 20.0 Hz); 130.0 (+, s, Cpara
2
of Ph in SiPh3); 92.2 (-, d, quaternary C in η5-C5H4, J CP
)
4.4 Hz); 91.2, 87.2, 85.1, 81.5 (+, all s, tertiary C’s in η5-C5H4);
1
28.7 (+, d, PCH, J CP ) 31.3 Hz); 20.6, 18.9 (+, both s,
PCHCH3); 1.6 (+, s, dCCH3). 31P{1H} NMR (121.4 MHz, C6D6,
293 K): δ 22.0 (s, d in off-resonance). MS (FAB+): m/z 792
(M+).
P r ep a r a tion of [OsH(η5-C5H4SiP h 3)(tCCH2P h )(P iP r 3)]-
BF 4 (7). To a solution of OsH(η5-C5H4SiPh3){dCdC(H)Ph}(Pi-
Pr3) (112 mg, 0.14 mmol) in 10 mL of diethyl ether was added
the stoichiometric amount of a 54% solution of HBF4 in diethyl
ether (20 µL, 0.15 mmol). The subsequent precipitate was
decanted and washed twice with diethyl ether (2 × 4 mL). A
dark brown solid was obtained. Yield: 108 mg (87%). Anal.
Calcd for C40H48BF4OsPSi: C, 55.55; H, 5.59. Found: C, 55.80;
H, 5.41. IR (Nujol, cm-1): ν(Os-H) 2071 (vw); ν(BF4) 1059 (m).
1H NMR (300 MHz, CDCl3, 293 K): δ 7.70-6.80 (20 H, Ph);
6.39-5.09 (ABCD system, 4 H, signals of η5-C5H4); 2.39 (s, 2
H, OstCCH2); 1.91 (m, 3 H, PCH); 1.08 (dd, 9 H, PCHCH3,
3
2
group, J HP < 1 Hz, J HH < 1 Hz); 2.15 (m, 3 H, PCH); 2.03
3
2
(dd, 1 H, one proton of the allyl group, J HP < 1 Hz, J HH < 1
3
Hz); 1.82 (dd, 1 H, one proton of the allyl group, J HP ) 18.3
Hz, J HH < 1 Hz); 1.12 (dd, 9 H, PCHCH3, J HP ) 14.1 Hz,
3
2
2J HH ) 7.2 Hz); 1.08 (dd, 9 H, PCHCH3, J HP ) 14.1 Hz, J HH
) 7.2 Hz); -13.37 (d, 1 H, OsH, 2J HP ) 30.0 Hz). 13C{1H} NMR
(75.5 MHz, CDCl3, 293 K, plus APT): δ 136.2, 128.4 (+, both
s, Cortho, Cmeta of Ph in SiPh3); 135.6 (-, s, Cipso of Ph in CPh);
131.9 (-, s, Cipso of Ph in SiPh3); 130.6 (+, s, Cpara in SiPh3);
129.9, 129.1 (+, both s, Cortho and Cmeta of Ph in CPh); 125.1
(+, s, Cpara of Ph in CPh); 106.7, 97.6, 88.9, 79.7 (+, all s,
tertiary C’s in η5-C5H4); 90.3 (-, s, quaternary C in η5-C5H4-
SiPh3); 86.2 (-, s, CPh); 28.4 (-, s, one of the secondary C
2
2
3
3
3J HP ) 15.9 Hz, J HH ) 7.2 Hz); 1.01 (dd, 9 H, PCHCH3, J HP
3
2
) 15.9 Hz, J HH ) 7.2 Hz); -12.00 (d, 1 H, OsH, J HP ) 24.3
1
Hz). 13C{1H} NMR (75.5 MHz, CDCl3, 293 K, plus APT): δ
atoms of the allyl group); 27.8 (+, d, PCH, J CP ) 30.6 Hz);
2
19.6, 19.1 (+, both s, PCHCH3); 18.7 (-, d, one of the secondary
290.6 (-, d, OstC, J CP ) 15.1 Hz); 136.1, 128.3 (+, both s,
ortho, Cmeta of Ph in SiPh3); 132.8 (-, s, Cipso of Ph in SiPh3);
C atoms of the allyl group, J CP ) 29.1 Hz). 31P{1H} NMR
2
C
(121.4 MHz, CDCl3, 293 K): δ 19.3 (s, d in off-resonance). MS
130.6 (+, s, Cpara of Ph in SiPh3); 129.1, 128.9 (+, both s, Cortho
and Cmeta of Ph in dCPh); 128.4 (-, s, Cipso of Ph in CH2Ph);
128.0 (+, s, Cpara of Ph in CH2Ph); 102.3, 94.3, 93.4, 90.5 (+,
all s, tertiary C’s in η5-C5H4); 88.4 (-, d, quaternary C in η5-
(FAB+): m/z 793 (M+).
P r ep a r a tion of [OsH(η5-C5H4SiP h 3){tCCD(CH3)P h }-
(P iP r 3)]BF 4 (8-d ). To a solution of OsH(η5-C5H4SiPh3){o-
C5H4, 2J CP ) 5.8 Hz); 57.5 (-, s, CH2); 30.1 (+, d, PCH, 1J CP
)
31.4 Hz); 19.2, 19.0 (+, both s, PCHCH3). 31P{1H} NMR (121.4
MHz, CDCl3, 293 K): δ 47.2 (s, d in off-resonance). MS
(FAB+): m/z 779 (M+).
C6H4C(CH3)dCH}(PiPr3) (102 mg, 0.13 mmol) in 10 mL of
diethyl ether was added the stoichiometric amount of a 1:1
mixture composed of a solution of HBF4 in diethyl ether and
deuterium oxide (D2O). The solution, which changed im-
mediately into a suspension, was vacuum-dried, and the
resulting residue washed with diethyl ether (3 × 4 mL),
leading to a white solid which was a 1:1 mixture of the two
pairs of enantiomers. Yield: 94 mg (82%). NMR data for pair
P r ep a r a tion of [OsH(η5-C5H4SiP h 3){tCCH(CH3)P h }-
(P iP r 3)]BF 4 (8). To a solution of OsH(η5-C5H4SiPh3){o-C6H4C-
(CH3)dCH}(PiPr3) (115 mg, 0.15 mmol) in 10 mL of diethyl
ether was added the stoichiometric amount of a 54% solution
of HBF4 in diethyl ether (20 µL, 0.15 mmol). The solution
changed immediately into a suspension. The solid was then
decanted and washed with diethyl ether (2 × 5 mL), leading
to a white solid which was a 1:1 mixture of the two pairs of
enantiomers. Yield: 110 mg (85%). Anal. Calcd for C41H50BF4-
OsPSi: C, 56.02; H, 5.73. Found: C, 56.18; H, 6.01. IR (KBr,
cm-1): ν(Os-H) 2180, 2128 (w); ν(BF4) 1054 (s). NMR data
1
a are as follows. H NMR (300 MHz, CDCl3, 293 K): δ 7.80-
6.80 (20 H, signals of Ph groups); 6.31-4.74 (ABCD system, 4
H, signals of η5-C5H4); 1.93 (m, 3 H, PCH); 1.30-0.80 (21H,
signals of PCHCH3 and CD(Ph)CH3); -11.59 (d, 1 H, OsH, 2J HP
) 24.9 Hz). 2H NMR (46.1 MHz, CHCl3, 293 K): δ 2.58 (s,
tCCD). 31P{1H} NMR (121.4 MHz, CDCl3, 293 K): δ 48.0 (s,
d in off-resonance). NMR data for pair b are as follows. 1H
NMR (300 MHz, CDCl3, 293 K): δ 7.80-6.80 (20 H, signals of
Ph groups); 6.61-4.65 (ABCD system, 4 H, signals of η5-C5H4);
1.84 (m, 3 H, PCH); 1.30-0.80 (21H, signals of PCHCH3 and
1
for pair a are as follows. H NMR (300 MHz, CDCl3, 293 K):
δ 7.80-6.80 (20 H, signals of Ph groups); 6.30-4.74 (ABCD
3
system, 4 H, signals of η5-C5H4); 2.47 (q, 1 H, tCCH, J HH
)
2
2
CD(Ph)CH3); -11.68 (d, 1 H, OsH, J HP ) 24.9 Hz). H NMR
(46.1 MHz, CHCl3, 293 K): δ 2.58 (s, tCCD). 31P{1H} NMR
(121.4 MHz, CDCl3, 293 K): δ 47.8 (s, d in off-resonance).
P r ep a r a t ion of [OsH (η5-C5H 4SiP h 3){η3-CH2C(C6H 4D)-
CH2}(P iP r 3)]BF 4 (9-d ). A solution of [OsH(η5-C5H4SiPh3)-
{tCCD(CH3)Ph}(PiPr3)]BF4 (12 mg) in 0.5 mL of chloroform-d
was heated to 42 °C over 72 h. 1H NMR (300 MHz, CDCl3,
293 K): δ 7.60-7.10 (19 H, signals of Ph groups); 6.77-3.27
(ABCD system, 4 H, signals of η5-C5H4); 4.46, 3.78 (both dd, 1
6.9 Hz); 1.93 (m, 3 H, PCH); 1.30-0.80 (21H, signals of
2
PCHCH3 and CH(Ph)CH3); -11.60 (d, 1 H, OsH, J HP ) 24.9
Hz). 13C{1H} NMR (75.5 MHz, CDCl3, 293 K): δ 294.2 (d, Ost
2
C, J CP ) 7.6 Hz); 137.0-127.0 (all s, C signals of Ph groups);
105.2, 93.5, 91.1, 88.7 (all s, tertiary C’s in η5-C5H4); 89.6 (d,
quaternary C in η5-C5H4SiPh3, 2J CP ) 4.3 Hz); 61.4 (s, tCCH);
1
30.0 (d, PCH, J CP ) 31.7 Hz); 20.0-19.0 (all s, signals of
PCHCH3); 16.5 (s, CH(Ph)CH3). 31P{1H} NMR (121.4 MHz,
CDCl3, 293 K): δ 47.9 (s). NMR data for pair b are as follows.
1H NMR (300 MHz, CDCl3, 293 K): δ 7.80-6.80 (20 H, signals
3
2
H each, two protons of the allyl group, J HP < 1 Hz, J HH < 1

Deprotonation of OsH(η5-C5H5)(CtCPh)(EPh3)(PiPr3)
Organometallics, Vol. 20, No. 23, 2001 4885
Ta ble 4. Cr ysta l Da ta a n d Da ta Collection a n d Refin em en t Deta ils for OsH(η5-C5H5)(CtCP h )(GeP h 3)(P iP r 3)
(4), OsH(η5-C5H4SiP h 3){o-C6H4C(CH3)dCH}(P iP r 3) (6), a n d [OsH(η5-C5H4SiP h 3){η3-CH2C(P h )CH2}(P iP r 3)]BF 4
(9)
4
6
9
Crystal Data
C41H49OsPSi
formula
mol wt
C
40H47GeOsP
C41H50BF4OsPSi‚CH2Cl2
963.81
821.54
791.06
color and habit
sym, space group
a, Å
b, Å
c, Å
yellow block
monoclinic, P21/c
11.0904(5)
19.2109(8)
16.5775(7)
90
97.017(1)
90
3505.5(3), 4
1.557
colorless block
monoclinic, P21/c
13.3545(9)
14.5873(12)
18.4672(12)
90
95.837(1)
90
3578.9(4), 4
1.468
colorless block
triclinic, P1h
11.7348(6)
12.2783(6)
16.9051(12)
101.215(1)
98.952(1)
115.796(1)
2070.0(2), 2
1.546
R, deg
â, deg
γ, deg
V, Å3; Z
D
calcd, g cm-3
Data Collection and Refinement
diffractometer
λ(Mo KR), Å
Bruker Smart APEX
0.710 73
graphite oriented
3.668
4 e 2θ e 60
296.0(2)
monochromator
µ, mm-1
2θ range, deg
temp, K
4.55
4 e 2θ e 60
296.0(2)
3.324
4 e 2θ e 60
173.0(2)
no. of data collected
no. of unique data (Rmerging
no. of params/restraints
R1a (F2 > 2σ(F2))
wR2b (all data)
Sc
31 992
8366 (0.0611)
398/1
0.0340
0.0541 (a ) 0.0180, b ) 0)
0.804
23 748
8499 (0.0807)
412/1
0.0424
0.0579 (a ) 0.0078, b ) 0)
0.684
19 647
9639 (0.0626)
496/1
0.0407
0.0762 (a ) 0.0255, b ) 0)
0.901
)
a
b
2
2
R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) {∑[w(Fo - Fc2)2]/∑[w(Fo2)2]}1/2; where w-1 ) σ2(Fo2) + ((aP)2 + bP, P ) (Fo + 2Fc2)/3. c GOF
) S ) {∑[w(Fo - Fc2)2]/(n - p)}1/2, where n is the number of reflections and p is the number of refined parameters.
2
3
Hz); 2.14 (m, 3 H, PCH); 2.03 (dd, 1 H, one proton of the allyl
2.07 (m, 3 H, PCH); 0.81 (dd, 9 H, PCHCH3, J HP ) 13.5 Hz,
3 3
3
2
group, J HP < 1 Hz, J HH < 1 Hz); 1.82 (dd, 1 H, one proton of
3J HH ) 6.9 Hz); 0.76 (dd, 9 H, PCHCH3, J HP ) 13.5 Hz, J HH
3
2
2
the allyl group, J HP ) 18.3 Hz, J HH < 1 Hz); 1.12 (dd, 9 H,
) 6.9 Hz). H NMR (46.1 MHz, C6H6, 293 K): δ 5.01 (s, 1 D,
2
2
PCHCH3, J HP ) 14.1 Hz, J HH ) 7.2 Hz); 1.08 (dd, 9 H,
η5-C5H4D); 3.21 (s, 1 D, OsdCdCD). 31P{1H} NMR (121.4 MHz,
C6D6, 293 K): δ 19.8 (s).
PCHCH3, 2J HP ) 14.1 Hz, 2J HH ) 7.2 Hz); -13.37 (d, 1 H, OsH,
2J HP ) 29.7 Hz). H NMR (46.1 MHz, CHCl3, 293 K): δ 7.35
P r ep a r a tion of Os(η5-C5H4CH3)(GeP h 3){dCdC(CH3)-
P h }(P iP r 3) (11). To a solution of OsH(η5-C5H5)(CtCPh)-
(GePh3)(PiPr3) (115 mg, 0.14 mmol) in 10 mL of THF was
added an excess of n-butyllithium (0.25 mL, 2.6 M, 0.65 mmol),
and the mixture was left to react for 10 min. Methyl iodide
(0.40 mL, 6.4 mmol) was then added, and the solution was
vacuum-dried. The resulting residue was washed with metha-
nol (3 × 3 mL), leading to a pale red solid. Yield: 86 mg (72%).
Anal. Calcd for C42H51GeOsP: C, 59.37; H, 6.05. Found: C,
59.71; H, 6.11. IR (Nujol, cm-1): ν(OsdCdC) 1625 (s). 1H NMR
(300 MHz, C6D6, 293 K): δ 8.00-6.80 (20 H, Ph); 5.01-4.07
(ABCD system, 4 H, signals of η5-C5H4); 2.45 (s, 3 H, dCCH3);
2.15 (m, 3 H, PCH); 1.95 (s, 3 H, η5-C5H4CH3); 0.83 (dd, 9 H,
2
(s, C6H4D). 31P{1H} NMR (121.4 MHz, CDCl3, 293 K): δ 19.3
(s, d in off-resonance).
P r epar ation of Os(η5-C5H5)(GeP h 3){dCdC(H)P h }(P iP r 3)
(10). To a solution of OsH(η5-C5H5)(CtCPh)(GePh3)(PiPr3) (176
mg, 0.21 mmol) in 15 mL of THF was added n-butyllithium
(0.25 mL, 2.6 M, 0.68 mmol), and the mixture was left to react
for 30 min. Methanol (1 mL) was then added, and the solution
was vacuum-dried. The resulting residue was washed with
methanol (3 × 3 mL), leading to a pale brown solid. Yield: 114
mg (65%). Anal. Calcd for C40H47GeOsP: C, 58.48; H, 5.77.
Found: C, 58.13; H, 5.47. IR (Nujol, cm-1): ν(OsdCdC) 1609
(s). 1H NMR (300 MHz, C6D6, 293 K): δ 7.90-6.80 (20 H, Ph);
5.04 (s, 5 H, η5-C5H5); 3.14 (d, 1 H, OsdCdCH, 4J HP ) 1.2 Hz);
3
3
PCHCH3, J HP ) 13.2 Hz, J HH ) 6.0 Hz); 0.81 (dd, 9 H,
3
3
3
2.07 (m, 3 H, PCH); 0.81 (dd, 9 H, PCHCH3, J HP ) 13.5 Hz,
PCHCH3, J HP ) 13.2 Hz, J HH ) 6.0 Hz). 13C{1H} NMR (75.5
3
3
2
3J HH ) 6.9 Hz); 0.76 (dd, 9 H, PCHCH3, J HP ) 13.5 Hz, J HH
MHz, C6D6, 293 K, plus APT): δ 304.3 (-, d, OsdC, J CP
)
) 6.9 Hz). 13C{1H} NMR (75.5 MHz, C6D6, 293 K, plus APT):
δ 299.5 (-, d, OsdC, J CP ) 12.0 Hz); 148.7 (-, s, Cipso Ph in
12.0 Hz); 150.2 (-, s, Cipso Ph in GePh3); 137.3, 127.6 (+, both
s, Cortho and Cmeta Ph in GePh3); 134.7 (-, s, Cipso Ph in dCPh);
128.2, 124.4 (+, both s, Cortho and Cmeta Ph in CPh); 127.5 (+,
s, Cpara Ph in GePh3); 124.1 (+, s, Cpara Ph in dCPh); 115.1 (-,
2
GePh3); 137.0, 127.7 (+, both s, Cortho and Cmeta Ph in GePh3);
131.5(-, s, Cipso Ph in dCPh); 128.7, 127.7 (+, both s, Cortho
and Cmeta Ph in CPh); 125.5 (+, s, Cpara Ph in GePh3); 124.2
(+, s, Cpara Ph in dCPh); 115.6 (+, s, OsdCdC); 84.9 (+, s,
s, OsdCdC); 100.4 (-, d, quaternary C in η5-C5H4CH3, 2J CP
)
6.0 Hz); 91.9, 86.3, 84.2, 80.5 (+, all s, tertiary C’s in η5-C5H4);
1
1
η5-C5H5); 30.6 (+, d, PCH, J CP ) 28.2 Hz); 21.0, 20.5 (+, both
30.8 (+, d, PCH, J CP ) 27.6 Hz); 20.9, 20.3 (+, both s,
s, PCHCH3). 31P{1H} NMR (121.4 MHz, C6D6, 293 K): δ 19.9
(s). MS (FAB+): m/z 822 (M+).
PCHCH3); 12.0, 8.7 (+, both s, CH3 in cyclopentadienyl and
vinylidene groups). 31P{1H} NMR (121.4 MHz, C6D6, 293 K):
δ 18.7 (s). MS (FAB+): m/z 850 (M+).
P r ep a r a t ion of Os(η5-C5H 4D)(GeP h 3){dCdC(D)P h }-
(P iP r 3) (10-d 2). To a solution of OsH(η5-C5H5)(CtCPh)-
(GePh3)(PiPr3) (125 mg, 0.15 mmol) in 10 mL of THF was
added n-butyllithium (0.15 mL, 2.6 M, 0.39 mmol), and the
mixture was left to react for 30 min. Methanol-d4 (0.5 mL) was
then added, and the solution was vacuum-dried. The resulting
residue was washed with methanol (3 × 2 mL), leading to a
pale brown solid. Yield: 75 mg (60%). 1H NMR (300 MHz,
C6D6, 293 K): δ 7.90-6.80 (20 H, -Ph); 5.04 (s, 4 H, η5-C5H4D);
P r ep a r a tion of [Os(η5-C5H5)(GeP h 3)(tCCH2P h )(P iP r 3)]-
BF 4 (12). To a solution of Os(η5-C5H5)(GePh3){dCdC(H)Ph}-
(PiPr3) (109 mg, 0.13 mmol) in 10 mL of diethyl ether was
added the stoichiometric amount of a 54% solution of HBF4 in
diethyl ether (20 µL, 0.15 mmol). The subsequent precipitate
was decanted and washed twice with diethyl ether (2 × 4 mL).
A pale brown solid was obtained. Yield: 100 mg (83%). Anal.
Calcd for C40H48BF4GeOsP: C, 52.82; H, 5.33. Found: C, 52.75;

4886 Organometallics, Vol. 20, No. 23, 2001
Baya et al.
H, 5.51. IR (Nujol, cm-1): ν(BF4) 1054 (s). 1H NMR (300 MHz,
CDCl3, 293 K): δ 7.50-7.00 (20 H, -Ph); 5.59 (5 H, s, η5-C5H5);
3.04 (part A of AB system, 1 H, OstCCH2, J AB ) 18.9 Hz);
2.85 (part B of AB system, 1 H, OstCCH2, J AB ) 18.9 Hz);
s, PCHCH3); 17.7, 13.6 (+, both s, signals of η5-C5H4CH3 and
CHCH3). 31P{1H} NMR (121.4 MHz, CDCl3, 293 K): δ 30.8 (s).
MS (FAB+): m/z 852 (M++H).
X-r a y Str u ctu r e An a lysis of Com p lexes OsH(η5-C5H5)-
3
2.27 (m, 3 H, PCH); 1.09 (dd, 9 H, PCHCH3, J HP ) 16.5 Hz,
(CtCP h )(GeP h 3)(P iP r 3) (4), OsH(η5-C5H4SiP h 3){o-C6H4C-
3
3
3J HH ) 7.5 Hz); 1.06 (dd, 9 H, PCHCH3, J HP ) 16.5 Hz, J HH
) 7.5 Hz). 13C{1H} NMR (75.5 MHz, CD3COCD3, 293 K, plus
APT): δ 297.6 (-, d, OstC, J CP ) 8.8 Hz); 144.3 (-, s, Cipso
(CH3)dCH}(P iP r 3) (6), a n d [OsH(η5-C5H4SiP h 3){η3-CH2C-
(P h )CH2}(P iP r 3)]BF 4 (9). Crystal data for 4, 6, and 9 were
measured on a Bruker Smart APEX diffractometer equipped
with a fine-focus, 2.4 kW sealed-tube X-ray source (molybde-
num radiation, λ ) 0.710 73 Å) operating at 50 kV and 30 mA
(4 and 9) or 50 kV and 35 mA (6). Data were collected over a
hemisphere by a combination of three sets. The cell parameters
were determined and refined by least-squares fits of 7187 (4),
2764 (6), and 6321 (9) collected reflections. Each frame
exposure was 10 s, covering 0.3° in ω. The first 100 frames
were collected at the end of the data collection to monitor
crystal decay. The absorption correction was made using a
multiscan method with SADABS.31 The structures were solved
by standard Patterson and conventional Fourier procedures.
The positions and anisotropic thermal parameters of the non-
hydrogen atoms were refined satisfactorily by full-matrix least-
squares calculations on F2 (SHELXL-97).31 In all cases the
hydride ligands were refined as free isotropic atoms converged
too close to the metal center. Finally, a mixed refinement with
the distance restrained to 1.59(1) Å was used (from the
Cambridge Crystallographic Data Center, mean of 81 terminal
osmium-hydride distances obtained by X-ray analysis).32
Crystal data and data collection and refinement details are
given in Table 4.
2
Ph in GePh3); 136.3 (-, s, Cipso Ph in CH2Ph); 136.2, 129.1 (+,
both s, Cortho and Cmeta Ph in GePh3); 130.7, 129.8 (+, both s,
Cortho and Cmeta Ph in CH2Ph); 129.8 (+, s, Cipso Ph in dCPh);
129.0 (+, s, Cpara in CH2Ph); 91.6 (+, s, η5-C5H5); 39.1 (-, s,
1
CH2); 31.8 (+, d, PCH, J CP ) 28.6 Hz); 20.8 (+, s, PCHCH3).
31P{1H} NMR (121.4 MHz, CDCl3, 293 K): δ 31.2 (s). MS
(FAB+): m/z 823 (M+).
P r ep a r a tion of [Os(η5-C5H4CH3)(GeP h 3){tCCH(CH3)-
P h }(P iP r 3)]BF 4 (13). To a solution of Os(η5-C5H4CH3)(GePh3)-
{dCdC(CH3)Ph}(PiPr3) (88 mg, 0.10 mmol) in 10 mL of diethyl
ether was added the stoichiometric amount of a 54% solution
of HBF4 in diethyl ether (15 µL, 0.11 mmol). The solution
changed immediately into a suspension, and the solid was
decanted and washed with diethyl ether (2 × 5 mL), leading
to a pale yellow solid which was a 2:1 mixture of the two pairs
of enantiomers. Yield: 84 mg (87%). Anal. Calcd for C42H52
-
BF4GeOsP: C, 53.81; H, 5.59. Found: C, 53.70; H, 5.79. IR
(Nujol, cm-1): ν(BF4) 1054 (s). NMR data for pair a was as
1
follows. H NMR (300 MHz, CDCl3, 293 K): δ 7.60-7.00 (20
H, signals of Ph groups); 6.32-5.00 (ABCD system, 4 H,
3
signals of η5-C5H4); 3.07 (q, 1 H, tCCH, J HH ) 7.2 Hz); 2.19
(m, 3 H, PCH); 1.71 (s, 3 H, η5-C5H4CH3); 1.26 (d, 3 H, CHCH3,
3J HH ) 7.2 Hz); 1.20-0.90 (18 H, signals of PCHCH3). 13C-
{1H} NMR (75.5 MHz, CDCl3, 293 K): δ 301.1 (-, d, OstC,
2J CP ) 8.3 Hz); 145.0-127.0 (all s, C signals of Ph groups);
110.2 (-, s, quaternary C in η5-C5H4CH3); 96.7, 91.9, 87.4, 83.0
(+, all s, tertiary C’s in η5-C5H4); 65.1 (+, s, tCCH); 30.9 (+,
d, PCH, 1J CP ) 28.8 Hz); 19.6, 19.5 (+, both s, PCHCH3); 16.7,
13.6 (+, both s, signals of η5-C5H4CH3 and CHCH3). 31P{1H}
NMR (121.4 MHz, CDCl3, 293 K): δ 28.6 (s). NMR data for
pair b are as follows. 1H NMR (300 MHz, CDCl3, 293 K): δ
Ack n ow led gm en t. We thank the DGES (Project
PB98-1591, Programa de Promocio´n General del Cono-
cimiento) for financial support. M.B. thanks the DGA
(Diputacio´n General de Arago´n) for a grant.
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates and equivalent isotropic displacement coefficients,
anisotropic thermal parameters, experimental details of the
X-ray studies, and bond distances and angles for 4, 6, and 9.
This material is available free of charge via the Internet at
http://pubs.acs.org.
7.60-7.00 (20 H, signals of Ph groups); 6.32-5.11 (ABCD
3
system, 4 H, signals of η5-C5H4); 3.40 (q, 1 H, tCCH, J HH
)
7.2 Hz); 2.24 (m, 3 H, PCH); 1.87 (s, 3 H, η5-C5H4CH3); 1.53
3
(d, 3 H, CHCH3, J HH ) 7.2 Hz); 1.20-0.90 (18 H, signals of
OM010504L
PCHCH3). 13C{1H} NMR (75.5 MHz, CDCl3, 293 K): δ 301.3
2
(31) Saint 5.0 and Shelxtl 6.1 Software Packages; Bruker AXS, Inc.,
Madison, WI, 2001.
(32) Allen, F. H.; Kennard, O. 3D Search and Research Using the
Cambridge Structural Database. Chemical Design Automation News
1993, 8(1), 31.
(-, d, OstC, J CP ) 8.3 Hz); 145.0-127.0 (all s, C signals of
Ph groups); 110.1 (-, s, quaternary C in η5-C5H4CH3); 96.2,
91.1, 87.4, 84.4 (+, all s, tertiary C’s in η5-C5H4); 64.6 (+, s,
1
tCCH); 30.8 (+, d, PCH, J CP ) 28.8 Hz); 19.9, 19.6 (+, both