A novel method to prepare hydride-phosphinito complexes

Article abstract of DOI:10.1021/om000446o

The cyclopentadienyl complex Os(if-CsHs)Cl(PlPr3)2 (1) reacts with diphenylphosphine to give the mixed-ligand compound OsOf-CsHClfPHPhPr (2). Treatment of 2 with TlPFe in humid acetone and in methanol affords the cationic dihydride complexes [OsU2Of-CsHPfOtyPhaypiPrMPFe (R = H (3), CH3 (4)), respectively. Similarly, the treatment of 2 with TIPF& in (CD3)2CO containing DO and in CDsOD gives the deuterated complexes. [OsHD(j]5'C5H{P(OE)Ph2}(P1' Pr3)]PF6 (R=D (3-d2), CD3 (4-d). The reaction of 3 with NaOCHs produces its deprotonation and the formation of the dihydride-phosphinito derivative OsH2~ (f-C5H5){P(O)Ph2}(PiPr3) (5). Under the same conditions, the deprotonation of 4 yields OsHOf-CsHs){P(OMe)Ph2}(PiPr3) (6) as a result of the extraction of one of the two hydrides. The treatment of 3-d2 with NaOMe selectively affords OsHD(if-C5H5){P(O)Ph2}(PiPra)(5-d).

Full text of DOI:10.1021/om000446o

4650
Organometallics 2000, 19, 4650-4652
A Novel Meth od To P r ep a r e Hyd r id e-P h osp h in ito
Com p lexes
Miguel A. Esteruelas,* Ana M. Lo´pez, J ose´ I. Tolosa, and Noelia Vela
Departamento de Quı´mica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received May 30, 2000
Summary: The cyclopentadienyl complex Os(η5-C5H5)-
Cl(PiPr3)2 (1) reacts with diphenylphosphine to give the
mixed-ligand compound Os(η5-C5H5)Cl(PHPh2)(PiPr3)
(2). Treatment of 2 with TlPF6 in humid acetone and in
methanol affords the cationic dihydride complexes [OsH2-
(η5-C5H5){P(OR)Ph2}(PiPr3)]PF6 (R ) H (3), CH3 (4)),
respectively. Similarly, the treatment of 2 with TlPF6 in
(CD3)2CO containing D2O and in CD3OD gives the
deuterated complexes [OsHD(η5-C5H5){P(OR)Ph2}(Pi-
Pr3)]PF6 (R ) D (3-d 2), CD3 (4-d 4)). The reaction of 3
with NaOCH3 produces its deprotonation and the for-
mation of the dihydride-phosphinito derivative OsH2-
(η5-C5H5){P(O)Ph2}(PiPr3) (5). Under the same condi-
tions, the deprotonation of 4 yields OsH(η5-C5H5)-
{P(OMe)Ph2}(PiPr3) (6) as a result of the extraction of
one of the two hydrides. The treatment of 3-d 2 with
NaOMe selectively affords OsHD(η5-C5H5){P(O)Ph2}(Pi-
Pr3) (5-d ).
a labile starting material for the development of new
cyclopentadienyl-osmium chemistry.4 The addition of
PPh3 to pentane solutions of 1 produces the displace-
ment of a triisopropylphosphine group to give Os(η5-
C5H5)Cl(PPh3)(PiPr3), which is a suitable compound for
studying the selectivity of the competitive alkane-arene
intramolecular C-H activation.5 Although the treat-
ment of 1 with TlPF6 produces the release of the chloro
and the methyl C-H activation of a triisopropylphos-
phine, the treatment of Os(η5-C5H5)Cl(PPh3)(PiPr3) with
TlPF6 gives rise to the release of the chloro ligand and
the ortho C-H activation of triphenylphosphine.
Similarly to the reaction of 1 with PPh3, the addition
of PHPh2 to pentane solutions of 1 affords Os(η5-
C5H5)Cl(PHPh2)(PiPr3) (2). Treatment of 2 with TlPF6
in humid acetone also produces the release of the
chlorine ligand; however, the C-H activation of a
Cortho-H bond of a phenyl group is not observed. Instead
of a C-H activation reaction, the formation of [OsH2-
(η5-C5H5){P(OH)Ph2}(PiPr3)]PF6 (3) takes place. The
generality of this reaction is evident in the synthesis of
[OsH2(η5-C5H5){P(OMe)Ph2}(PiPr3)]PF6 (4), which is
prepared by treatment of 2 with TlPF6 in methanol
(Scheme 1).
The oxidative addition of the P-H bond of diphe-
nylphosphine oxide to platinum(0) and palladium(0)
complexes has been previously the method used to
prepare hydride-phosphinito derivatives. Although the
formation of these compounds is one of the key steps in
the stereoselective hydrophosphinylation of alkynes,
affording alkenylphosphine oxides,1 only a few hydride-
phosphinito transition-metal compounds have been
reported. As far as we know, they are monohydride-
platinum(II) and -palladium(II) derivatives, where the
phosphinito ligand is stabilized by an electrostatic
interaction between the oxygen atom and a Lewis acid.2
In general, this acid is the hydrogen atom of a diphe-
nylphosphine oxide cis-disposed to the phosphinito
group.2b-d
We now report a novel method to prepare hydride-
phosphinito complexes. The new strategy leds to OsH2-
(η5-C5H5){P(O)Ph2}(PiPr3), which is the first hydride-
phosphinito compound stabilized by a transition metal
different from platinum and palladium, and where the
phosphinito ligand is not stabilized by an oxygen-Lewis
acid interaction.
The presence of a P(OH)Ph2 ligand in 3 is strongly
supported by the IR and 1H NMR spectra of this
compound. The IR spectrum in Nujol shows a ν(OH)
1
band at 3467 cm-1, whereas the H NMR spectrum in
CD2Cl2 at 193 K contains a broad signal at 4.92 ppm,
corresponding to the OH proton. Furthermore, in the
high-field region, the spectrum shows a double doublet
at -12.97 ppm both having J (HP) values of 28.8 Hz,
which agree well with a four-legged piano-stool geom-
etry around the metallic center, with mutually transoid
hydrides that are cisoid-disposed to the phosphorus
1
donor ligands.6 The H and 31P{1H} NMR spectra of 4
are also in accordance with the structure proposed for
this compound in Scheme 1.
When the treatment of 1 with TlPF6 was carried out
in (CD3)2CO containing D2O and in CD3OD, the deu-
Despite the high kinetic stability of the OsCpL3
compounds,3 we have described overwhelming evidence
showing that the complex Os(η5-C5H5)Cl(PiPr3)2 (1) is
(4) (a) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Oro, L. A.
Organometallics 1996, 15, 878. (b) Esteruelas, M. A.; Lo´pez, A. M.;
Ruiz, N.; Tolosa, J . I. Organometallics 1997, 16, 4657. (c) Crochet, P.;
Esteruelas, M. A.; Gutie´rrez-Puebla, E. Organometallics 1998, 17,
3141. (d) Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa,
J . I. Organometallics 1998, 17, 3479. (e) Baya, M.; Crochet, P.;
Esteruelas, M. A.; Gutie´rrez-Puebla, E.; Ruiz, N. Organometallics 1999,
18, 5034.
(5) Esteruelas, M. A.; Gutie´rrez-Puebla, E.; Lo´pez, A. M.; On˜ate, E..;
Tolosa, J . I. Organometallics 2000, 19, 275.
(6) The mentioned J (HP) values are typical for this arrangement.
See for example refs 4e and 5 and: (a) Rottink, M. K.; Angelici, R. J .
J . Am. Chem. Soc. 1993, 115, 7267. (b) Wanandi, P. W.; Tilley, T. D.
Organometallics 1997, 16, 4299.
(1) Han, L.-B.; Tanaka, M. Chem. Commun. 1999, 395.
(2) (a) Beaulieu, W. B.; Rauchfuss, T. B.; Roundhill, D. M. Inorg.
Chem. 1975, 14, 1732. (b) van Leeuwen, P. W. N. M.; Roobeek, C. F.;
Wife, R. L.; Frijns, J . H. G. J . Chem. Soc., Chem. Commun. 1986, 31.
(c) van Leeuwen, P. W. N. M.; Roobeek, C. F.; Orpen, A. G. Organo-
metallics 1990, 9, 2179. (d) Han, L.-B.; Choi, N.; Tanaka, M. Organo-
metallics 1996, 15, 3259.
(3) Atwood, J . D. Inorganic and Organometallic Reaction Mecha-
nisms; VCH: New York, 1997; Chapter 3.
10.1021/om000446o CCC: $19.00 © 2000 American Chemical Society
Publication on Web 09/26/2000

Notes
Organometallics, Vol. 19, No. 22, 2000 4651
Sch em e 1
Treatment of 3 with NaOMe in THF produces its
deprotonation and the formation of the dihydride-
phosphinito-osmium(IV) derivative OsH2(η5-C5H5)-
{P(O)Ph2}(PiPr3) (5). Under the same conditions, the
deprotonation of 4 yields OsH(η5-C5H5){P(OMe)Ph2}(Pi-
Pr3) (6) as a result of the extraction of one of the two
hydrides (Scheme 1).
The most noticeable feature in the IR spectrum of 5
in KBr are the absence of any ν(OH) band and the
presence of two absorptions at 1105 and 1047 cm-1 due
to the PdO bond.9 In the 1H NMR spectrum, the hydride
ligands give rise to a double doublet with J (HP) values
of 26.1 and 29.7 Hz, which are in agreement with the
structure proposed for 5 in Scheme 1.
The deprotonation of 4 to give 6 could suggest that
the formation of 5 proceeds by extraction of a hydride
of 3 and subsequent 1,3-hydrogen migration from the
oxygen atom of the OH group to the osmium. However,
the treatment of 3-d 2 with NaOMe selectively affords
OsHD(η5-C5H5){P(O)Ph2}(PiPr3) (5-d ), indicating that
the deprotonation of 3 is a one-step process and occurs
at the OH group of the P(OH)Ph2 ligand (eq 1).
Sch em e 2
The presence of a deuteride ligand in 5-d is supported
by the 2H NMR spectrum of this compound, which
contains a broad singlet at -13.07 ppm.
In conclusion, the oxidative addition of the P-H bond
of secondary phosphines to unsaturated complexes
followed by the addition of water and deprotonation of
the resulting P(OH)Ph2 ligand is a useful method to
prepare hydride-phosphinito complexes.
terated complexes [OsHD(η5-C5H5){P(OD)Ph2}(PiPr3)]-
PF6 (3-d 2) and [OsHD(η5-C5H5){P(OCD3)Ph2}(PiPr3)]PF6
(4-d 4) were obtained, respectively (Scheme 2). The
presence of a deuterium atom at the oxygen of 3-d 2 is
supported by the IR spectrum of this compound in Nujol,
which shows a ν(OD) band at 2535 cm-1, whereas the
presence of a deuterium atom at the metallic center of
both 3-d 2 and 4-d 4 is supported by the 2H NMR spectra,
which contain a double doublet at -12.78 (3-d 2) and
-12.60 (4-d 4) ppm, with J (DP) values of 4.3 (3-d 2) and
4.7 (4-d 4) Hz.
Exp er im en ta l Section
All reactions were carried out with exclusion of air using
standard Schlenk techniques. Solvents were dried by known
procedures and distilled under argon prior to use. The starting
material Os(η5-C5H5)Cl(PiPr3)2 (1) was prepared by the pub-
lished method.4b
In the NMR spectra, chemical shifts are expressed in ppm
downfield from Me4Si (1H and 13C) and 85% H3PO4 (31P).
P r ep a r a tion of Os(η5-C5H5)Cl(P HP h 2)(P iP r 3) (2). A sus-
pension of 1 (200 mg, 0.33 mmol) in 15 mL of pentane was
treated with PHPh2 (56.4 µL, 0.33 mmol). After the mixture
The distribution of deuterium atoms in 3-d 2 and 4-d 4
indicates the following.
(i) The formation of 3 and 4 takes place via the
hydride-phosphido intermediate [OsH(η5-C5H5)(PPh2)(Pi-
Pr3)]+. This species is generated by intramolecular P-H
oxidative addition of diphenylphosphine in the unsatur-
ated [Os(η5-C5H5)(PHPh2)(PiPr3)]+ metallic fragment.7
Once the hydride-phosphido species is formed, the
RO-H addition to the Os-phosphido bond affords 3
and 4.8
(7) The oxidative addition of the P-H bond of secondary phosphines
to unsaturated transition-metal complexes is a well-known process of
interest in connection with the catalytic phosphination and hydro-
phosphination of olefins. See for example: (a) Wicht, D. K.; Kourkine,
I. V.; Lew, B. M.; Nthenge, J . M.; Glueck, D. S. J . Am. Chem. Soc.
1997, 119, 5039. (b) Kourkine, I. V.; Sargent, M. D.; Glueck, D. S.
Organometallics 1998, 17, 125. (c) Wicht, D. K.; Paisner, S. N.; Lew,
B. M.; Glueck, D. S.; Yap, G. P. A.; Liable-Sands, L. M.; Rheingold, A..
L.; Haar, C. M.; Nolan, S. P. Organometallics 1998, 17, 652. (d) Wicht,
D. K.; Kovacik, I.; Glueck, D. S.; Liable-Sands, L. M.; Incarvito, C. D.;
Rheingold, A. L. Organometallics 1999, 18, 5141. (e) Wicht, D. K.;
Kourkine, I. V.; Kovacik, I.; Glueck, D. S.; Concolino, T. E.; Yap, G. P.
A.; Incarvito, C. D.; Rheingold, A. L.Organometallics 1999, 18, 5381.
(8) Similar additions of methanol and water across a WdP bond
have been reported. See for example: (a) J o¨rg, K.; Malisch, W.; Reich,
W.; Meyer, A.; Schubert, U. Angew. Chem., Int. Ed. Engl. 1986, 25,
92. (b) Malisch, W.; Hirth, U.-A.; Gru¨n, K.; Schmeusser, M.; Fey, O.;
Weis, U. Angew. Chem., Int. Ed. Engl. 1995, 34, 2500.
(ii) The P-H oxidative addition in [Os(η5-C5H5)-
(PHPh2)(PiPr3)]+ is favored with regard to the methyl
C-H activation of triisopropylphosphine and the ortho
C-H activation of diphenylphosphine. This suggests
that, under strictly the same metal ligand system, the
M-P-H oxidative addition is favored with regard to the
alkyl metalation and aryl ortho metalation.
(9) Malisch, W.; Hindahl, K.; Gru¨n, K.; Adam, W.; Prechtl, F.;
Sheldrick, W. S. J . Organomet. Chem. 1996, 509, 209.

4652 Organometallics, Vol. 19, No. 22, 2000
Notes
was stirred for 5 h at room temperature, the solvent was
partially evaporated until a yellow solid precipitated, which
was washed with 3 mL of cold pentane and dried in vacuo.
described for 4, starting from 2 and methanol-d4 as solvent.
1H NMR (300 MHz, CD2Cl2, 293 K): δ 7.62-7.54 (m, 10 H,
Ph), 5.20 (s, 5 H, Cp), 2.08 (m, 3 H, PCH), 1.17 (dd, J (HH) )
7.2 Hz, J (PH) ) 15.0 Hz, 18 H, PCCH3), -12.75 (dd, J (PH) )
27.9 Hz, J (PH) ) 28.8 Hz, 1 H, OsH). H NMR (46.07 MHz,
CH2Cl2, 293 K): 3.31 (d, J (PD) ) 1.9 Hz, 3 H, OCD3), -12.60
(dd, J (PD) ) 4.7, J (PD) ) 4.7, Hz, OsD).
P r ep a r a t ion of OsH 2(η5-C5H 5){P (O)P h 2}(P iP r 3) (5). A
solution of 3 (100 mg, 0.13 mmol) in 10 mL of THF was treated
with NaOMe (10.6 mg, 0.20 mmol). The mixture was stirred
for 5 h at room temperature. The yellow solution obtained was
concenterated to dryness, and 10 mL of toluene was added.
The suspension was filtered through Kieselguhr, and the
solvent was removed in vacuo. Addition of pentane caused the
precipitation of a yellow solid, which was washed with pentane
and dried in vacuo. Yield: 85.6 mg (94%). IR (KBr): ν(OsH)
2129, ν(PO) 1105, 1047 cm-1. 1H NMR (300 MHz, CD2Cl2, 293
K): δ 7.57 (m, 4 H, Ph), 7.26-7.18 (m, 6 H, Ph), 4.94 (s, 5 H,
Cp), 2.00 (m, 3 H, PCH), 1.06 (dd, J (HH) ) 7.2 Hz, J (PH) )
14.4 Hz, 18 H, PCCH3), -13.31 (dd, J (PH) ) 26.1 Hz, J (PH)
) 29.7 Hz, 2 H, OsH2). 31P{1H} NMR (121.42 MHz, CD2Cl2,
293 K): δ 38.9 (d, J (PP) ) 20.4 Hz, P(O)Ph2), 34.8 (d, J (PP) )
20.4 Hz, PiPr3). Anal. Calcd for C26H38OOsP2: C, 50.47; H, 6.19.
Found: C, 50.39; H, 6.00. MS (FAB+): m/e 619 (M+ + H).
1
Yield: 180 mg (86%). IR (Nujol): ν(PH) 2292 cm-1. H NMR
2
(300 MHz, C6D6, 293 K): δ 7.81 (d, J (PH) ) 352.2 Hz, 1 H,
PH), 7.76 (m, 2 H, Ph), 7.32 (m, 2 H, Ph), 7.09-6.94 (m, 6 H,
Ph), 4.58 (s, 5 H, Cp), 2.39 (m, 3 H, PCH), 1.17 (dd, J (HH) )
7.1 Hz, J (PH) ) 13.4 Hz, 9 H, PCCH3), 0.83 (dd, J (HH) ) 7.1
Hz, J (PH) ) 13.4 Hz, 9 H, PCCH3). 31P{1H} NMR (121.42 MHz,
C6D6, 293 K): δ 12.1 (d, J (PP) ) 22.6 Hz, PiPr3), -5.8 (d, J (PP)
) 22.6 Hz, PHPh2). Anal. Calcd for C26H37ClOsP2: C, 49.01;
H, 5.85. Found: C, 48.86; H, 5.76. MS (FAB+): m/e 638 (M+).
P r ep a r a tion of [OsH2(η5-C5H5){P (OH)P h 2}(P iP r 3)]P F 6
(3). A solution of 2 (140 mg, 0.22 mmol) in 15 mL of acetone
was treated with TlPF6 (76.7 mg, 0.22 mmol). After the
mixture was stirred for 15 min at room temperature, the
suspension obtained was filtered through Kieselguhr and the
solvent was removed in vacuo. The addition of diethyl ether
caused the precipitation of a white solid, which was washed
whith diethyl ether and dried in vacuo. Yield: 160 mg (95%).
1
IR (Nujol): ν(OH) 3467, ν(PF6) 840 cm-1. H NMR (300 MHz,
CD2Cl2, 293 K): δ 7.62-7.55 (m, 6 H, Ph), 7.47-7.40 (m, 4 H,
Ph), 5.22 (s, 5 H, Cp), 1.85 (m, 3 H, PCH), 1.08 (dd, J (HH) )
6.9 Hz, J (PH) ) 14.7 Hz, 18 H, PCCH3), -12.97 (dd, J (PH) )
28.8 Hz, J (PH) ) 28.8 Hz, 2H, OsH2). 1H NMR (300 MHz, CD2-
Cl2, 193 K): δ 4.92 (br, P(OH)). 31P{1H} NMR (121.42 MHz,
C6D6, 293 K): δ 83.2 (d, J (PP) ) 20.4 Hz, P(OH)Ph2), 40.6 (d,
J (PP) ) 20.4 Hz, PiPr3). Anal. Calcd for C26H39OOsP3F6: C,
40.83; H, 5.14. Found: C, 41.14; H, 5.32. MS (FAB+): m/e 619
(M+).
P r ep a r a tion of OsHD(η5-C5H5){P (O)P h 2}(P iP r 3) (5-d ).
The compound 5-d was prepared analogously as described for
1
5, starting from 3-d 2. H NMR (300 MHz, CD2Cl2, 293 K): δ
7.57 (m, 4 H, Ph), 7.26-7.18 (m, 6 H, Ph), 4.94 (s, 5 H, Cp),
2.00 (m, 3 H, PCH), 1.06 (dd, J (HH) ) 7.2 Hz, J (PH) ) 14.4
Hz, 18 H, PCCH3), -13.31 (dd, J (PH) ) 26.1 Hz, J (PH) ) 29.7
P r ep a r a tion of [OsHD(η5-C5H5){P (OD)P h 2}(P iP r 3)]P F 6
(3-d 2). The compound 3-d 2 was prepared analogously as
described for 3, starting from 2 and a mixture of 15 mL of
acetone-d6 and 0.1 mL of D2O as solvent. IR (Nujol): ν(OD)
2
Hz, 1 H, OsH). H NMR (46.07 MHz, CH2Cl2, 293 K): -13.07
(br, OsD).
P r ep a r a tion of OsH(η5-C5H5){P (OMe)P h 2}(P iP r 3) (6).
A solution of 4 (100 mg, 0.13 mmol) in 10 mL of THF was
treated with NaOMe (10.6 mg, 0.20 mmol). The mixture was
stirred for 5 h at room temperature. The yellow solution
obtained was concenterated to dryness, and 10 mL of toluene
was added. The suspension was filtered through Kieselguhr,
and the solvent was removed in vacuo. Addition of methanol
caused the precipitation of a yellow solid, which was washed
with methanol and dried in vacuo. Yield: 58 mg (72%). IR
1
2535, ν(PF6) 840 cm-1. H NMR (300 MHz, CD2Cl2, 293 K): δ
7.62-7.55 (m, 6 H, Ph), 7.47-7.40 (m, 4 H, Ph), 5.22 (s, 5 H,
Cp), 1.85 (m, 3 H, PCH), 1.08 (dd, J (HH) ) 6.9 Hz, J (PH) )
14.7 Hz, 18 H, PCCH3), -12.97 (dd, J (PH) ) 28.8 Hz, J (PH)
2
) 28.8 Hz, 1 H, OsH). H NMR (46.07 MHz, CH2Cl2, 293 K):
-12.78 (dd, J (PD) ) 4.3 Hz, J (PD) ) 4.3 Hz, OsD).
P r ep a r a tion of [OsH2(η5-C5H5){P (OMe)P h 2}(P iP r 3)]P F 6
(4). A solution of 2 (140 mg, 0.22 mmol) in 15 mL of methanol
was treated with TlPF6 (76.7 mg, 0.22 mmol). After the
mixture was stirred for 15 min at room temperature, the
suspension obtained was filtered through Kieselguhr and the
solvent was removed in vacuo. The addition of diethyl ether
caused the precipitation of a white solid, which was washed
with diethyl ether and dried in vacuo. Yield: 161.1 mg (94%).
IR (Nujol): ν(OsH) 2154, ν(PF6) 840 cm-1. 1H NMR (300 MHz,
CD2Cl2, 293 K): δ 7.62-7.54 (m, 10 H, Ph), 5.20 (s, 5 H, Cp),
3.38 (d, J (PH) ) 12.3 Hz, 3 H, OCH3), 2.08 (m, 3 H, PCH),
1.17 (dd, J (HH) ) 7.2 Hz, J (PH) ) 15.0 Hz, 18 H, PCCH3),
-12.75 (dd, J (PH) ) 27.9 Hz, J (PH) ) 28.8 Hz, 2 H, OsH2).
31P{1H} NMR (121.42 MHz, C6D6, 293 K): δ 100.6 (d, J (PP) )
18.2 Hz, P(OMe)Ph2), 41.1 (d, J (PP) ) 18.2 Hz, PiPr3). Anal.
Calcd for C27H41OOsP3F6: C, 41.64; H, 5.31. Found: C, 42.11;
H, 5.39. MS (FAB+): m/e 635 (M+).
1
(Nujol): ν(OsH) 2083 cm-1. H NMR (300 MHz, CD2Cl2, 293
K): δ 7.73-7.65 (m, 4 H, Ph), 7.28-7.09 (m, 6 H, Ph), 4.61 (s,
5 H, Cp), 3.60 (d, J (PH) ) 12.9 Hz, 3 H, OCH3), 1.57 (m, 3 H,
PCH), 0.97 (dd, J (HH) ) 5.4 Hz, J (PH) ) 11.6 Hz, 9 H,
PCCH3), 0.95 (dd, J (HH) ) 6.6 Hz, J (PH) ) 12.3 Hz, 9 H,
PCCH3), -15.96 (dd, J (PH) ) 27.8 Hz, J (PH) ) 27.8 Hz, 1 H,
OsH). 31P{1H} NMR (121.42 MHz, CD2Cl2, 293 K): δ 106.3
(d, J (PP) ) 16.8 Hz, P(OMe)Ph2), 38.6 (d, J (PP) ) 16.8 Hz,
PiPr3). Anal. Calcd for C27H40OOsP2: C, 51.25; H, 6.37.
Found: C, 51.23; H, 6.28. MS (FAB+): m/e 635 (M++ H).
Ack n ow led gm en t. We thank the DGES (Project
PB-98-1591, Programa de Promocio´n General del Cono-
cimiento) for financial support.
P r ep a r a tion of [OsHD(η5-C5H5){P (OCD3)P h 2}(P iP r 3)]-
P F 6 (4-d 4). The compound 4-d 4 was prepared analogously as
OM000446O