Sequential protonation and methylation of a hydride-osmium complex containing a cyclopentadienyl ligand with a pendant amine group

Article abstract of DOI:10.1021/ic0502933

Complex OsH{η⁵-C₅H₄(CH ₂)₂NMe₂}(PⁱPr₃) ₂ (1) reacts with 1 equiv of trifluoromethanesulfonic acid (HOTf) and trifluoromethanesulfonic acid-d₁ (DOTf) to produce the dihydride and hydride-deuteride complexes, [OsHE{η⁵-C₅H ₄(CH₂)₂NMe₂}(PⁱPr ₃)₂]OTf (E = H (2), D (2-d₁)), respectively. Treatment of 2 and 2-d₁ with a second equivalent of HOTf gives [OsHE[η⁵-C₅H₄(CH₂) ₂NHMe₂}(PⁱPr₃)₂][OTf] ₂ (E = H (3), D (3-d₁)) as a result of the protonation of the nitrogen atom. While the hydride and deutende ligands of 2, 2-d₁, 3, and 3-d₁ do not undergo any H/D exchange process with the solvent, in acetone-d₆ the NH proton of 3 and 3-d₁ changes places with a deuterium atom of the solvent to yield [OsHE{η⁵- C₅H₄(CH₂)₂NDMe₂}(P ⁱPr₃)₂][OTf]₂ (E = H (3-Nd ₁), D (3-d₂)). Complex 3-Nd₁ can also be obtained from the treatment of complex 2 with DOTf in dichloromethane. No exchange process between the hydride and the ND positions in 3-Nd₁ or between the deuteride and NH positions in 3-d₁ has been observed. Treatment of 3-Nd₁ and 3-d₁ with sodium methoxide results in a selective reaction of the base with the ammonium group to regenerate 2 and 2-d₁, respectively. Complex 1 also reacts with methyl and methyl-d₃ trifluoromethanesulfonate (CH₃OTf and CD ₃OTf, respectively) to give [OsH{η⁵-C ₅H₄(CH₂)₂NMe₂CE ₃}(PⁱPr₃)₂]OTf (E = H (4), D (4-d₃)) as a result of the addition of the CE₃ (E = H, D) group to the nitrogen atom. Complex 4 has been characterized by an X-ray diffraction analysis. It reacts with a second molecule of CH₃OTf or CD₃OTf to produce [OsH{η⁵-C₅H ₄(CH₂)₂-NMe₃}{CH ₂CH(CH₃)PⁱPr₂}(PⁱPr ₃)][OTf]₂ (5). Similarly, complex 4-d₃ reacts with a second molecule of CH₃OTf or CD₃OTf to yield [OsH{η⁵-C₅H₄(CH₂) ₂NMe₂CD₃}{CH₂CH(CH ₃)PⁱPr₂}(PⁱPr₃)][OTf] ₂ (5-d₃). In acetonitrile, complex 5 evolves to an equilibrium mixture of the acetonitrile adducts [Os{η⁵-C ₅H₄(CH₂)₂NMe₃}(NCCH ₃)(PⁱPr₃)₂][OTf]₂ (7) and [Os{η⁵-C₅H₄(CH₂) ₂NMe₃}(NCCH₃)₂(PⁱPr ₃)][OTf]₂ (8). In methanol or methanol-d₄, complex 4 is not stable and loses trimethylamine to give the vinylcyclopentadienyl derivatives [OsHE(η⁵-C₅H ₄CH=CH₂)(PⁱPr₃)₂]OTf (E = H (9), D (9-d₁)) as a result of the protonation or deuteration of the metallic center and a subsequent Hofmann elimination. Protonation of 4 with HOTf gives the dihydride-trimethylammonium derivative [OsH₂{η ⁵-C₅H₄(CH₂)₂NMe ₃}(PⁱPr₃)₂]-[OTf]₂ (10). Treatment of 9 with sodium methoxide produces OsH(η⁵-C ₅H₄CH=CH₂)(PⁱPr₃) ₂ (11).

Full text of DOI:10.1021/ic0502933

Inorg. Chem. 2005, 44, 4094−4103
Sequential Protonation and Methylation of a Hydride
−Osmium Complex
Containing a Cyclopentadienyl Ligand with a Pendant Amine Group
Miguel A. Esteruelas,* Ana M. Lo´pez, Enrique On˜ate, and Eva Royo
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
UniVersidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received February 25, 2005
Complex OsH{η5-C5H4(CH2)2NMe2
trifluoromethanesulfonic acid-d1 (DOTf) to produce the dihydride and hydride
C5H4(CH2)2NMe2 H (2), D (2-d1)), respectively. Treatment of 2 and 2-d1 with a second equivalent
(PiPr3)2]OTf (E
of HOTf gives [OsHE{η5-C5H4(CH2)2NHMe2 (PiPr3)2][OTf]2 (E
H (3), D (3-d1)) as a result of the protonation of
}
(PiPr3)2 (1) reacts with 1 equiv of trifluoromethanesulfonic acid (HOTf) and
−
deuteride complexes, [OsHE{η5
-
}
)
}
)
the nitrogen atom. While the hydride and deuteride ligands of 2, 2-d1, 3, and 3-d1 do not undergo any H/D exchange
process with the solvent, in acetone-d6, the NH proton of 3 and 3-d1 changes places with a deuterium atom of the
} ) H (3-Nd1), D (3-d2)). Complex 3-Nd1 can also be
solvent to yield [OsHE{η5-C5H4(CH2)2NDMe2 (PiPr3)2][OTf]2 (E
obtained from the treatment of complex 2 with DOTf in dichloromethane. No exchange process between the hydride
and the ND positions in 3-Nd1 or between the deuteride and NH positions in 3-d1 has been observed. Treatment
of 3-Nd1 and 3-d1 with sodium methoxide results in a selective reaction of the base with the ammonium group to
regenerate 2 and 2-d1, respectively. Complex 1 also reacts with methyl and methyl-d3 trifluoromethanesulfonate
} ) H (4), D (4-d3)) as a
(CH3OTf and CD3OTf, respectively) to give [OsH{η5-C5H4(CH2)2NMe2CE3 (PiPr3)2]OTf (E
result of the addition of the CE3 (E H, D) group to the nitrogen atom. Complex 4 has been characterized by an
)
X-ray diffraction analysis. It reacts with a second molecule of CH3OTf or CD3OTf to produce [ OsH{η5-C5H4(CH2)2-
NMe3}{CH2CH(CH3)PiPr2 (PiPr3)][OTf]2 (5). Similarly, complex 4-d3 reacts with a second molecule of CH3OTf or
CD3OTf to yield [OsH{η5-C5H4(CH2)2NMe2CD3}{CH2CH(CH3)PiPr2 (PiPr3)][OTf]2 (5-d3). In acetonitrile, complex 5
evolves to an equilibrium mixture of the acetonitrile adducts [Os{η5-C5H4(CH2)2NMe3 (NCCH3)(PiPr3)2][OTf]2 (7)
and [Os{η5-C5H4(CH2)2NMe3 (NCCH3)2(PiPr3)][OTf]2 (8). In methanol or methanol-d4, complex 4 is not stable and
loses trimethylamine to give the vinylcyclopentadienyl derivatives [OsHE( H (9),
5-C5H4CH CH2)(PiPr3)2]OTf (E
D (9-d1)) as a result of the protonation or deuteration of the metallic center and a subsequent Hofmann elimination.
Protonation of 4 with HOTf gives the dihydride
trimethylammonium derivative [OsH2{η5-C5H4(CH2)2NMe3 (PiPr3)2]-
[OTf]2 (10). Treatment of 9 with sodium methoxide produces OsH(
5-C5H4CH CH2)(PiPr3)2 (11).
}
}
}
}
η
d
)
−
}
η
d
Introduction
The intramolecular cleavage of η2-H2 is a result of its
deprotonation by the basic site of a coligand.5 Then, H+ and
H- are transferred to the substrate.6 The catalyst is regener-
ated by coordination of molecular hydrogen to the metal4,5
(Scheme 1).
Cyclopentadienyl ligands bearing pendant donor groups
are attracting increased interest from those who study the
chemistry of metals.1 Complexes with this type of ligand
are expected to perform chemistry in a manner different from
that of usual cyclopentadienyl complexes.2 Indeed, the
presence of the pendant donor group facilitates the study of
some reaction mechanisms.3
Formic acid has been obtained by reduction of car-
bon dioxide with molecular hydrogen in the presence of
[Ru{η5-C5H4(CH2)nNMe2}(dppm)]BF4 (n ) 2 or 3, dppm
There is increasing evidence showing that polar CdX
bonds (X ) N, O) can be reduced by an ionic mechanism.4
(1) (a) Jutzi, P.; Siemeling, U. J. Organomet. Chem. 1995, 500, 175. (b)
Jutzi, P.; Redeker, T. Eur. J. Inorg. Chem. 1998, 663. (c) Butenscho¨n,
H. Chem. ReV. 2000, 100, 1527. (d) Qian, Y.; Huang, J.; Bala, M. D.;
Lian, B.; Zhang, H.; Zhang, H. Chem. ReV. 2003, 103, 2633.
* To whom correspondence should be addressed. E-mail: maester@
posta.unizar.es.
4094 Inorganic Chemistry, Vol. 44, No. 11, 2005
10.1021/ic0502933 CCC: $30.25
© 2005 American Chemical Society
Published on Web 05/05/2005

Hydride-Osmium Complex
Scheme 1
of the metal center. The replacement of the dppm ligand by
the more weakly donating triphenyl phosphite ligands results
in the RuH{η5-C5H4(CH2)nNHMe2}{P(OPh)3}2 species (n )
2) in which no Ru-H‚‚‚H-N dihydrogen-bonding interac-
tion is present between the hydride and the ammonium
proton.9 Sabo-Etienne, Chaudret, and co-workers have
reported that the related triphenylphosphine derivative RuH-
{η5-C5H4(CH2)2NMe2}(PPh3)2 reacts with [HNEt3][BPh4] or
[HPBu3][BPh4] to produce [RuH{η5-C5H4(CH2)2NHMe2}-
(PPh3)2]+, which also undergoes a proton-hydride intramo-
lecular exchange process. However, in this case, the inter-
mediacy of a η2-dihydrogen tautomer does not seem to be
necessary. In agreement with this, the addition of HBF4 to
RuH{η5-C5H4(CH2)2NMe2}(PPh3)2 promotes the loss of
) Ph2PCH2PPh2) complexes.7 The proposed catalytic cycle8
is similar to that shown in Scheme 1. The proposal is sup-
ported by the observation that the addition of HBF4 to
the RuH{η5-C5H4(CH2)nNMe2}(dppm) monohydrides leads
to the intramolecular dihydrogen-bonded Ru-H‚‚‚H-N
[RuH{η5-C5H4(CH2)nNHMe2}(dppm)]BF4 complexes, which
show rapid and reversible hydride-proton exchange via the
intermediacy of the η2-dihydrogen [Ru{η5-C5H4(CH2)n-
NMe2}(η2-H2)(dppm)]BF4 tautomers.7 The strength of the
Ru-H‚‚‚H-N interaction is very sensitive to the basicity
molecular hydrogen and the formation of [Ru{η5-C5H4-
(CH2)2NMe2}(PPh3)2]BF4.10
For the iron triad, numerous iron and ruthenium com-
plexes containing a cyclopentadienyl ligand with a pen-
dant donor group have been reported.1c However, the os-
mium counterparts are very scarce, and they were unknown
until very recently.2j As a part of our work on the osmium
cyclopentadienyl unit,11 we have recently described the
preparation of the first osmium compounds containing a
cyclopentadienyl ligand with a pendant donor group,2j,12
including the synthesis of the monohydride OsH{η5-
C5H4(CH2)2NMe2}(PiPr3)2.12 We are now interested in de-
termining how the change from ruthenium to osmium
influences the chemistry of the half-sandwich cyclopenta-
dienyl complexes. Thus, we have studied the behavior of
the latter monohydride toward electrophiles. In this paper,
we report the reactions of OsH{η5-C5H4(CH2)2NMe2}(PiPr3)2
with HOTf, DOTf, CH3OTf, and CD3OTf as well as the
(2) For examples, see: (a) Kettenbach, R. T.; Bonrath, W.; Butenscho¨n,
H. Chem. Ber. 1993, 126, 1657. (b) Mobley, T. A.; Bergman, R. J.
Am. Chem. Soc. 1998, 120, 3253. (c) Van der Zeijden, A. A. H.;
Jime´nez, J.; Mattheis, C.; Wagner, C.; Merzweiler, K. Eur. J. Inorg.
Chem. 1999, 1919. (d) Klei, S. R.; Tilley, T. D.; Bergman, R. G.
Organometallics 2002, 21, 4905. (e) Daugulis, O.; Brookhart, M.;
White, P. S. Organometallics 2003, 22, 4699. (f) Yong, L.; Hofer,
E.; Wartchow, R.; Butenscho¨n, H. Organometallics 2003, 22, 5463.
(g) Becker, E.; Mereiter, K.; Puchberger, M.; Schmid, R.; Kirchner,
K.; Doppiu, A.; Salzer, A. Organometallics 2003, 22, 3164. (h)
Esteruelas, M. A.; Ferna´ndez, F. J.; Lo´pez, A. M.; On˜ate, E.
Organometallics 2003, 22, 1787. (i) Webster, C. E.; Hall, M. B. Coord.
Chem. ReV. 2003, 238-239, 315. (j) Esteruelas, M. A.; Lo´pez, A.
M.; On˜ate, E.; Royo, E. Organometallics 2004, 23, 3021.
(3) For examples, see: (a) Liang, Y.; Yap, G. P. A.; Rheingold, A. L.;
Theopold, K. H. Organometallics 1996, 15, 5284. (b) Emrich, R.;
Heinemann, O.; Jolly, P. W.; Kru¨ger, C.; Verhovnik, G. P. J.
Organometallics 1997, 16, 1511. (c) Do¨hring, A.; Go¨hre, J.; Jolly, P.
W.; Kryger, B.; Rust, J.; Verhovnik, G. P. J. Organometallics 2000,
19, 388. (d) Jensen, V. R.; Angermund, K.; Jolly, P. W.; Børve, K. J.
Organometallics 2000, 19, 403. (e) Enders, M.; Ferna´ndez, P.; Ludwig,
G.; Pritzkow, H. Organometallics 2001, 20, 5005. (f) Do¨hring, A.;
Jensen, V. R.; Jolly, P. W.; Thiel, W.; Weber, J. C. Organometallics
2001, 20, 2234.
(9) Lam, Y. F.; Yin, C.; Yeung, C. H.; Ng, S. M.; Jia, G.; Lau, C. P.
Organometallics 2002, 21, 1898.
(10) Ayllon, J. A.; Sayers, S. F.; Sabo-Etienne, S.; Donnadieu, B.; Chaudret,
B.; Clot, E. Organometallics 1999, 18, 3981.
(11) (a) Esteruelas, M. A.; Gomez, 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. (f) Esteruelas, M. A.; Gutie´rrez-Puebla, E.; Lo´pez,
A. M.; On˜ate, E.; Tolosa, J. I. Organometallics 2000, 19, 275. (g)
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. (h) Esteruelas, M. A.; Lo´pez, A. M.; Tolosa, J. I.;
Vela, N. Organometallics 2000, 19, 4650. (i) Baya, M.; Crochet,
P.; Esteruelas, M. A.; On˜ate, E. Organometallics 2001, 20, 240. (j)
Baya, M.; Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Modrego,
J.; On˜ate, E. Organometallics 2001, 20, 4291. (k) Baya, M.; Esteruelas,
M. A.; On˜ate, E. Organometallics 2001, 20, 4875. (l) Carbo´, J.
J.; Crochet, P.; Esteruelas, M. A.; Jean, Y.; Lledo´s, A.; Lo´pez, A.
M.; On˜ate, E. Organometallics 2002, 21, 305. (m) Baya, M.;
Esteruelas, M. A. Organometallics 2002, 21, 2332. (n) Baya, M.;
Esteruelas, M. A.; On˜ate, E. Organometallics 2002, 21, 5681. (o)
Esteruelas, M. A.; Gonza´lez, A. I.; Lo´pez, A. M.; On˜ate, E.
Organometallics 2003, 22, 414. (p) Baya, M.; Buil, M. L.; Esteruelas,
M. A.; On˜ate, E. Organometallics 2004, 23, 1416. (q) Esteruelas, M.
A.; Gonza´lez, A. I.; Lo´pez, A. M.; On˜ate, E. Organometallics 2004,
23, 4858.
(4) Papish, E. T.; Magee, M. P.; Norton, J. R. In Recent AdVances in
Hydride Chemistry; Peruzzini, M., Poli, R., Eds.; Elsevier: Amsterdam,
The Netherlands, 2001; Chapter 2, pp 39-74.
(5) (a) Jessop, P. G.; Morris, R. H. Coord. Chem. ReV. 1992, 121, 155.
(b) Heinekey, D. M.; Oldham, W. J., Jr. Chem. ReV. 1993, 93, 913.
(c) Morris, R. H. In Recent AdVances in Hydride Chemistry; Peruzzini,
M., Poli, R., Eds.; Elsevier: Amsterdam, The Netherlands, 2001;
Chapter 1, pp 1-38.
(6) For examples, see: (a) Gaus, P. L.; Kao, S. C.; Youngdahl, K.;
Darensbourg, M. Y. J. Am. Chem. Soc. 1985, 107, 2428. (b) Gibson,
D. H.; El-Omrani, Y. S. Organometallics 1985, 4, 1473. (c) Geraty,
S. M.; Harkin, P.; Vos, J. G. Inorg. Chim. Acta 1987, 131, 217. (d)
Bullock, R. M.; Rappoli, B. J. J. Chem. Soc., Chem. Commun. 1989,
1447. (e) Song, J. S.; Szalda, D. J.; Bullock, R. M.; Lawrie, C. J. C.;
Rodkin, M. A.; Norton, J. R. Angew. Chem., Int. Ed. Engl. 1992, 31,
1233. (f) Bullock, R. M.; Song, J.-S. J. Am. Chem. Soc. 1994, 116,
8602. (g) Minato, M.; Fujiwara, Y.; Itu, T. Chem. Lett. 1995, 647. (h)
Bakhmutov, V. I.; Vorontsov, E. V.; Antonov, D. Y. Inorg. Chim.
Acta 1998, 278, 122. (i) Minato, M.; Fujiwara, Y.; Koga, M.;
Matsumoto, N.; Kurishima, S.; Natori, M.; Sekizuka, N.; Yoshioka,
K.; Ito, T. J. Organomet. Chem. 1998, 569, 139. (j) Samec, J. S. M.;
Ba¨ckvall, J.-E. Chem.sEur. J. 2002, 8, 2955. (k) Barrio, P.; Esteruelas,
M. A.; On˜ate, E. Organometallics 2004, 23, 3627.
(7) Chu, H. S.; Lau, C. P.; Wong, K. Y.; Wong, W. T. Organometallics
1998, 17, 2768.
(8) (a) Matsubara, T. Organometallics 2001, 20, 19. (b) Matsubara, T.;
Hirao, K. Organometallics 2001, 20, 5759.
(12) Esteruelas, M. A.; Lo´pez, A. M.; On˜ate, E.; Royo, E. Organometallics
2004, 23, 5633.
Inorganic Chemistry, Vol. 44, No. 11, 2005 4095

Esteruelas et al.
Scheme 2
2 with DOTf in dichloromethane. In acetone, complex 3-Nd1
regenerates 3. The presence of a deuterium at the nitrogen
atom of 3-Nd1 is strongly supported not only by the absence
1
of any NH resonance in the H NMR spectrum of this
compound but also by the presence of a broad singlet at 8.90
2
ppm in the H NMR spectrum in dichloromethane. The
chemical shifts of the resonance of the NH proton in acetone-
d6 (3) or the ND deuterium atom in acetone (3-Nd1) are
dependent on the sample concentration because of the
NH‚‚‚OdC(CD3)2 and ND‚‚‚OdC(CH3)2 interactions, re-
spectively. The influence of sample concentration on these
chemical shifts is not observed in dichloromethane, in
which no H-D exchange is observed. This suggests that
NH‚‚‚OdC(CD3)2 and ND‚‚‚OdC(CH3)2 interactions are the
first step in the H-D exchanges between the ammonium
group and the oxygenated solvent, which could occur accord-
ing to the mechanism previously proposed by Bianchini.13
In dichloromethane-d2 and acetone-d6, exchange between
the hydride positions of 3-Nd1 and the deuterium at the
nitrogen atom is not observed. Any preference of the metallic
center for the hydrogen atom must be excluded. Indeed, the
addition of 1.0 equiv of DOTf to dichloromethane solutions
of 1 leads to the hydride-deuteride [OsHD{η5-C5H4(CH2)2-
2
NMe2}(PiPr3)2]OTf (2-d1), which is seen in the H NMR
spectrum as a triplet at -13.80 ppm with a 2J(DP) coupling
constant of 4.1 Hz. Exchange between the deuteride position
and the solvent is not observed either in dichloromethane or
in acetone.
dehydroamination reaction on the pendant substituent of the
cyclopentadienyl ligand.
Complex 2-d1 in dichloromethane reacts with 1.0 equiv
of HOTf to produce [OsHD{η5-C5H4(CH2)2NHMe2}(PiPr3)2]-
[OTf]2 (3-d1) as a result of the protonation of the nitrogen
atom of 2-d1. Exchange between the deuteride and NH posi-
tions, in dichloromethane-d2 or acetone-d6, is not observed.
In acetone-d6, the NH proton exchanges with a deuterium
atom of the solvent to give [OsHD{η5-C5H4(CH2)2NDMe2}(Pi-
Pr3)2][OTf]2 (3-d2), which contains deuterium at both the
metallic center and the nitrogen atom of the pendant group.
The reactions shown in Scheme 2 merit further comment.
Complex 1 contains three basic sites, namely, the metal, the
hydride, and the amino group, each one able to react with
an electrophile, in this case the proton. The results collected
in Scheme 2 clearly indicate that, from a thermodynamic
point of view, the preference of each site for the proton
decreases in the following sequence: metal > amino group
> hydride. This is in contrast with the results obtained from
the theoretical calculations on the ruthenium-monohydride
RuH{η5-C5H4(CH2)2NMe2}(PH3)2, which do not show any
strong thermodynamic preference for one site.10
Results and Discussion
1. Reactions of OsH{η5-C5H4(CH2)2NMe2}(PiPr3)2 (1)
with HOTf and DOTf. The investigations that aimed to
elucidate the behavior of 1 in the presence of HOTf and
DOTf are summarized in Scheme 2.
Between -80 °C and room temperature, the addition of
1.0 equiv of HOTf to dichloromethane solutions of 1 results
in the instantaneous and quantitative formation of dihydride
[OsH2{η5-C5H4(CH2)2NMe2}(PiPr3)2][OTf]2 (2), which is
represented by a triplet at -14.19 ppm with a 2J(HP)
coupling constant of 29.1 Hz in the H NMR spectrum. In
dichloromethane-d2 and in acetone-d6, exchange between the
hydride positions and the solvent is not observed.
The addition of 1.0 equiv of HOTf to dichloromethane
solutions of 2 leads to the formation of [OsH2{η5-C5H4(CH2)2-
NHMe2}(PiPr3)2][OTf]2 (3) as result of the protonation of
the nitrogen atom of the pendant group. The most noticeable
1
1
resonances of this compound in the H NMR spectrum in
We have also observed that complex 1 reacts with triethyl-
ammonium tetraphenylborate in dichloromethane to give
[OsH2{η5-C5H4(CH2)2NMe2}(PiPr3)2]BPh4 (2-BPh4), and tri-
ethylamine (eq 1), which is in agreement with the thermody-
namic preference of the metallic center over the amino group.
dichloromethane-d2 are a broad singlet at 8.94 ppm, corre-
sponding to the NH proton, and a triplet, assigned to the
2
hydride ligands, at -14.19 ppm with a J(HP) coupling
constant of 28.8 Hz. These signals are temperature invariant
between -80 °C and room temperature.
In contrast to the hydride ligands, in acetone-d6 at room
temperature, the NH proton of complex 3 undergoes an H-D
exchange process with the solvent to produce the monodeu-
terated derivative [OsH2{η5-C5H4(CH2)2NDMe2}(PiPr3)2]-
[OTf]2 (3-Nd1), which can also be obtained by treatment of
4096 Inorganic Chemistry, Vol. 44, No. 11, 2005

Hydride-Osmium Complex
Scheme 3
Figure 1. Molecular diagram of the cation of [OsH{η5-C5H4(CH2)2-
NMe3}(PiPr3)]2OTf (4). Thermal ellipsoids are shown at 50% prob-
ability.
Table 1. Selected Bond Distances (Å) and Angles (deg) for Complex
[OsH{η5-C5H4(CH2)2NMe3}(PiPr3)2]OTf (4)
Os-P(1)
Os-P(2)
Os-C(1)
Os-C(2)
Os-C(3)
Os-C(4)
Os-C(5)
2.3002(8)
2.2928(8)
2.222(3)
2.246(3)
2.271(3)
2.231(3)
2.225(3)
Os-H(01)
N-C(7)
1.45(3)
1.508(3)
1.489(4)
1.500(3)
1.489(4)
1.510(4)
1.515(4)
N-C(8)
N-C(9)
N-C(10)
C(1)-C(6)
C(6)-C(7)
In addition, the deprotonation of the ammonium group is
not only thermodynamically but also kinetically favored in
comparison with the deprotonation of the osmium atom.
Thus, treatment at room temperature of the tetrahydrofuran
solutions of 3-Nd1 with 1.0 equiv of sodium methoxide
regenerates 2. Deuterium is not observed at the hydride
positions. In agreement with this, the addition of sodium
methoxide to 3-d1 in THF selectively yields 2-d1.
P(1)-Os-P(2)
P(1)-Os-Ma
104.14(3)
124.2
85.1(10)
124.8
77.4(11)
127.0
N-C(7)-C(6)
C(7)-N-C(8)
C(7)-N-C(9)
C(7)-N-C(10)
C(8)-N-C(9)
C(8)-N-C(10)
115.8(2)
111.5(2)
107.3(2)
111.1(2)
108.5(2)
109.9(2)
P(1)-Os-H(01)
P(2)-Os-Ma
P(2)-Os-H(01)
Ma-Os-H(01)
C(9)-N-C(10)
108.4(2)
a M represents the midpoint of the C(1)-C(5) Cp ligand.
2. Reactions of 1 with CH3OTf and CD3OTf. In contrast
to the reaction with 1.0 equiv of HOTf, the treatment at room
temperature of dichloromethane solutions of 1 with 1.0 equiv
of CH3OTf promotes the quaternization of the amino group
of the pendant substituent as a consequence of the addition
of the methyl group to the nitrogen atom (Scheme 3).
The formation of [OsH{η5-C5H4(CH2)2NMe3}(PiPr3)2]OTf
(4) suggests that, in complex 1, the nitrogen atom is the
kinetically favored site for the electrophilic addition. Com-
plex 4 was isolated as a white solid in almost quantitative
of the phosphine ligands, which experience a large steric
hindrance as a consequence of their large cone angle (160°).14
Thus, the P-Os-P angle (104.14(3)°) strongly deviates from
the ideal value of 90°. P-M-P angles similar to those of 4
have previously been found in the square-planar complexes
Rh(acac)(PCy3)2 (105.63(4)°),15 Rh(κ2-O2CCH3)(PiPr3)2
(106.00(4)°),16 and [Ir(TFB)(PiPr3)2]BF4 (TFB ) tetrafluo-
robarralene, 102.7(1)°),17 the five-coordinate derivative
[Rh(acac){(E)-CHdCHCy}(PCy3)2]BF4 (105.3(1)°),15 and
the octahedral compounds [Os(κ2-O2CCH3){C(Me)C(OH)-
MePh}(PiPr3)2]BF4 (103.71(6)°)18 and Os{η2-CH2dCHC-
1
yield and characterized by elemental analysis, IR, H, 13C-
{1H}, and 31P{1H} NMR spectroscopy, and X-ray diffraction
analysis. A drawing of the cation of 4 is shown in Figure 1.
Selected bond distances and angles are listed in Table 1.
The structure shows that there is a quaternary ammonium
group in the complex; it has a tetrahedral arrangement around
the nitrogen atom with C-N-C angles between 107.3(2)°
and 111.5(2)°. The geometry around the osmium center can
be described as a very distorted octahedron with the
cyclopentadienyl ring occupying the three sites of a face.
The distortion is mainly caused by the mutual cis disposition
(OH)Ph2}(κ2-O2CCH3)(PiPr3)2 (106.72(4)°).18
In agreement with the presence of a hydride ligand in 4,
its IR spectrum in Nujol shows a ν(Os-H) band at 2052
(14) Tolman, C. A. Chem. ReV. 1977, 77, 313.
(15) Esteruelas, M. A.; Lahoz, F. J.; On˜ate, E.; Oro, L. A.; Rodr´ıguez, L.;
Steinert, P.; Werner, H. Organometallics 1996, 15, 3436.
(16) Werner, H.; Scha¨fer, M.; Nu¨rnberg, O.; Wolf, J. Chem. Ber. 1994,
127, 27.
(17) Chen, W.; Esteruelas, M. A.; Herrero, J.; Lahoz, F. J.; Martin, M.;
On˜ate, E.; Oro, L. A. Organometallics 1997, 16, 6010.
(18) Buil, M. L.; Esteruelas, M. A.; Garc´ıa-Yebra, C.; Guitie´rrez-Puebla,
E.; Oliva´n, M. Organometallics 2000, 19, 2184.
(13) Bianchini, C.; Linn, K.; Masi, D.; Peruzzini, M.; Polo, A.; Vacca, A.;
Zanobini, F. Inorg. Chem. 1993, 32, 2366.
Inorganic Chemistry, Vol. 44, No. 11, 2005 4097

Esteruelas et al.
1
cm-1. In the H NMR spectrum in acetone-d6 at room
Scheme 4
temperature, the hydride ligand results in a triplet at -15.68
2
ppm with a J(HP) coupling constant of 30.6 Hz. The
31P{1H} NMR spectrum shows a singlet at 32.9 ppm.
Complex 4 reacts with a second molecule of CH3OTf. The
treatment at room temperature of dichloromethane solutions
of the monohydride with 1.0 equiv of the electrophile
produces, in an 83% yield, the white metalated derivative
[Os{η5-C5H4(CH2)2NMe3}{CH2CH(CH3)PiPr2}(PiPr3)]-
[OTf]2 (5). This compound was isolated as a 1:1 equilibrium
mixture19 of stereoisomers 5a and 5b shown in Scheme 3.
In solution, the presence of isomers 5a and 5b is strongly
supported by the H, 13C{1H}, and 31P{1H} spectra of 5. In
1
Scheme 5
the 1H NMR spectrum in acetone-d6, the hydride resonances
appear at -13.96 and -13.70 ppm as a doublet of doublets
2
with J(HP) coupling constants of 34.8 and 26.0 Hz, and
36.8 and 28.8 Hz, respectively. In the 13C{1H} NMR
spectrum, the Os-CH2 and PCH signals of the metalated
isopropyl group are observed at -27.1 and 49.9 ppm, and
-27.0 and 47.6 ppm, respectively. These chemical shifts
agree well with those previously reported for the com-
plexes [OsH(η5-C5H5){CH2CH(CH3)PiPr2}(PiPr3)]PF6 (-36.9
and 49.9 ppm and -37.4 and 46.9 ppm),11b [{CH2CH-
(CH3)iPr2P}OsH{η5-C5H4(CH2)2PPh2}]PF6 (-22.5 and 46.6
ppm and -24.3 and 43.4 ppm),2j RuH(η5-C5H5){CH2CH-
(CH3)PiPr2}(SiMePh2) (-31.5 and 42.8 ppm),20 and RuH-
The formation of 5 takes place via the unsaturated
intermediate 6 (Scheme 4), which can be trapped as a 2:1
equilibrium mixture of adducts [Os{η5-C5H4(CH2)2NMe3}-
(NCCH3)(PiPr3)2][OTf]2 (7) and [Os{η5-C5H4(CH2)2NMe3}-
(NCCH3)2(PiPr3)][OTf]2 (8). Adducts 7 and 8 were fully char-
(η6-C6H6){CH2CH(CH3)PiPr2} (-10.7 and 42.8 ppm).21 The
31P{1H} NMR spectrum shows four doublets for isomers 5a
and 5b at 11.4 and -29.5 ppm, and 10.1 and -31.3 ppm,
with 2J(PP) coupling constants of 26 and 21 Hz, respectively.
Complex 5 is certainly the result of the reaction of an
external methyl group with the hydride ligand of 4 and the
subsequent C-H activation of an isopropyl group of one of
the phosphine ligands. Thus, we have observed that 5 can
be also obtained by addition of 1.0 equiv of CD3OTf to
dichloromethane solutions of 4. The formation of a metalated
species containing a CD3 group at the ammonium fragment,
1
acterized by H, 13C{1H}, and 31P{1H} NMR spectroscopy.
In the 1H NMR spectrum of the mixture, the most
noticeable feature is the absence of any hydride resonance
and the presence of a triplet at 2.82 ppm and a doublet at
5
2.66 ppm both with J(HP) coupling constants of 1.2 Hz,
corresponding to the acetonitrile ligands of 7 and 8,
respectively. The 13C{1H} NMR spectrum for the acetonitrile
ligand of 7 shows a broad triplet at 96.0 ppm and a singlet
at 5.2 ppm; they were assigned to the C(sp) atom and the
CH3 group, respectively. The resonances of the acetonitrile
ligands present in 8 appear as a doublet at 88.7 ppm, with a
3J(CP) coupling constant of 7.0 Hz, and a singlet at 4.5 ppm.
The 31P{1H} NMR spectrum contains singlets at 0.0 and 17.5
ppm corresponding to 7 and 8, respectively.
[OsH{η5-C5H4(CH2)2NMe2CD3}{CH2CH(CH3)PiPr2}(PiPr3)]-
[OTf]2, in spectroscopically detectable concentrations, does
not take place. This complex, 5-d3 in Scheme 3, was obtained
in a two-step procedure via the monohydride intermediate
[OsH{η5-C5H4(CH2)2NMe2CD3}(PiPr3)2]OTf (4-d3), which is
a result of the addition of 1.0 equiv of CD3OTf to a
dichloromethane solution of 1. The presence of a CD3 group
at the ammonium fragments of 4-d3 and 5-d3 is strongly
supported by the 2H NMR spectra of these compounds, which
show singlets at 3.49 and 3.22 ppm, respectively.
3. Reactions of 4 with CH3OH and CD3OD: Dehy-
droamination of the Pendant Substituent. In methanol, the
monohydride-osmium(II) complex, 4, is unstable and
evolves into trimethylamine and the dihydride-osmium(IV)
vinylcyclopentadienyl derivative [OsH2(η5-C5H4CHdCH2)-
(PiPr3)2]OTf (9), which was isolated as a white solid in a
68% yield (Scheme 5). The presence of a vinyl substituent
at the cyclopentadienyl ligand of 9 is strongly supported by
(19) When the reaction was carried out in toluene, a white solid was formed.
Its NMR spectra in CD2Cl2 revealed the presence of 5a and 5b in a
9:1 molar ratio. After 5 h at room temperature, the 1:1 equilibrium
mixture is reached.
(20) Campion, B. K.; Heyn, R. H.; Tilley, T. D.; Rheingold, A. L. J. Am.
Chem. Soc. 1993, 115, 5527.
1
the H and 13C{1H} NMR spectra of this compound. In the
1H NMR spectrum in dichloromethane-d2 at room temper-
ature, the -CHd resonance of the vinyl group appears at
3
(21) Kletzin, H.; Werner, H. Angew. Chem., Int. Ed. Engl. 1983, 22, 873.
6.40 ppm as a doublet of doublets with J(HH) coupling
4098 Inorganic Chemistry, Vol. 44, No. 11, 2005

Hydride-Osmium Complex
constants of 17.6 and 10.8 Hz, whereas the dCH2 resonances
are observed as doublets at 5.64 (trans to H) and 5.43 (cis
to H) ppm. In the high field region, the spectrum shows a
triplet at -14.22 ppm, corresponding to the hydride ligands,
with a 2J(HP) coupling constant of 29.2 Hz. In the 13C{1H}
NMR spectrum, the vinyl resonances are observed as singlets
at 127.3 (CH) and 120.5 (CH2) ppm. The 31P{1H} NMR
spectrum contains a singlet at 32.2 ppm.
hydride ligand appears as a triplet at -16.67 ppm with a
2J(HP) coupling constant of 31.6 Hz. In the 13C{1H} NMR
spectrum, the vinyl group is represented by singlets at 134.5
(CH) and 107.9 (CH2) ppm. The 31P{1H} NMR spectrum
shows a singlet at 27.7 ppm. The reaction shown in eq 3 is
reversible. Thus, the addition of 1.0 equiv of NaOTf to a
methanol solution of 11 produces 9.
Concluding remarks
In methanol-d4, complex 4 produces [OsHD(η5-C5H4CHd
CH2)(PiPr3)2]OTf (9-d1) which contains a deuterium atom
at the position of one of the hydride ligands of 9. Its presence
This study revealed that complex OsH{η5-C5H4(CH2)2-
NMe2}(PiPr3)2 has two nucleophilic centers, which undergo
attack by electrophiles, such as proton and methyl groups.
From a thermodynamic point of view, the protonation of the
metallic center is preferred over that of the nitrogen atom.
Thus, complex OsH{η5-C5H4(CH2)2NMe2}(PiPr3)2 reacts
with HOTf to give [OsH2{η5-C5H4(CH2)2NMe2}(PiPr3)2]OTf
and [OsH2{η5-C5H4(CH2)2NHMe2}(PiPr3)2][OTf]2 in a se-
quential manner. However, from a kinetic point of view, the
addition of electrophiles to the nitrogen atom appears to be
favored with regard to the osmium atom. In agreement with
this, complex OsH{η5-C5H4(CH2)2NMe2}(PiPr3)2 reacts with
CH3OTf to produce [OsH{η5-C5H4(CH2)2NMe3}(PiPr3)2]OTf
as result of the addition of the methyl group to the nitrogen
atom. Treatment of the latter complex with a second molecule
of CH3OTf promotes the attack of a new methyl group, now
to the osmium atom. As a result of this addition and the
subsequent elimination of methane, the unsaturated inter-
mediate [Os{η5-C5H4(CH2)2NMe3}(PiPr3)2]2+ is formed. This
2
is supported by the H NMR spectrum in dichloromethane
which contains a triplet at -14.13 ppm with a 2J(DP)
coupling constant of 4 Hz.
The position of the deuterium atom in 9-d1 suggests that
the transformation from 4 to 9 is a one-pot synthesis of two
reactions. They are the protonation of the metallic center by
action of methanol and a Hofmann elimination22 on the
ammonium group, promoted by the methoxide anion which
was generated from the metal protonation. We have also
observed that the addition of 1.0 equiv of HOTf to dichlo-
romethane solutions of 4 yields dihydride [OsH2{η5-
C5H4(CH2)2NMe3}(PiPr3)2][OTf]2 (10 in eq 2) and treatment
of 10 with 1.0 equiv of sodium methoxide in tetrahydrofuran
produces 9, which supports the proposed mechanism.
short-lived species evolves into [Os{η5-C5H4(CH2)2NMe3}-
{CH2CH(CH3)PiPr2}(PiPr3) by methyl C-H activation of an
isopropyl group of one of the phosphine ligands.
Complex 10 was isolated as a white solid in a 90% yield
1
In methanol, the metallic center of [OsH{η5-C5H4(CH2)2-
NMe3}(PiPr3)2]OTf undergoes the attack of a proton from
the solvent to yield the dicationic dihydride complex [OsH2-
{η5-C5H4(CH2)2NMe3}(PiPr3)2]2+. The oxidation of the os-
mium atom results in an acidity increase of the Cp-CH2 group
of the cyclopentadienyl chain, which becomes higher than
that of the OsH2 unit. Thus, the first deprotonation of
dihydride [OsH2{η5-C5H4(CH2)2NMe3}(PiPr3)2]2+ occurs at
the Cp-CH2 group. As a consequence of this extraction,
trimethylamine is eliminated from the pendant substituent,
and the dihydride vinylcyclopentadienyl derivative [OsH2-
(η5-C5H4CHdCH2)(PiPr3)2]+ is formed. The deprotonation
of the latter (second deprotonation) gives the monohydride
OsH(η5-C5H4CHdCH2)(PiPr3)2.
and characterized by MS, elemental analysis, IR, and H,
13C{1H}, and 31P{1H} NMR spectroscopy. The most notice-
1
able feature of this compound, in the H NMR spectrum in
acetone-d6 at room temperature, is a triplet at -14.09 ppm
2
with a J(HP) coupling constant of 29.2 Hz. The 31P{1H}
NMR spectrum contains a singlet at 32.8 ppm.
Unlike the OsH2 unit of 10, the OsH2 unit of 9 can be
deprotonated. Treatment of 9 with 1.1 equiv of sodium
methoxide in tetrahydrofuran produces monohydride OsH-
(η5-C5H4CHdCH2)(PiPr3)2 (11), which was isolated as a
yellow solid in a 64% yield (eq 3).
In conclusion, we showed that in an osmium hydride
complex containing a cyclopentadienyl ligand with an amino
pendant substituent, both the amino group and the metallic
center undergo sequential protonation and methylation.
Furthermore, the pendant group is transformed into a vinyl
substituent by a Hofmann elimination of amine, which is
promoted by the oxidation of the metallic center.
1
In the H NMR spectrum of 11 in benzene-d6 at room
temperature, the -CHd resonance of the vinyl substituent
of the cyclopentadienyl ligand appears at 6.55 ppm as a
doublet of doublets with 3J(HH) coupling constants of 17.2
and 10.8 Hz, whereas the dCH2 resonances are observed at
5.22 (trans to H) and 5.0 (cis to H) ppm as doublets. The
Experimental Section
General Information. All manipulations were performed using
an argon vacuum manifold and standard Schlenk techniques.
Solvents were dried by known procedures and were used freshly
(22) March, J.; Smith, M. B. AdVanced Organic Chemistry: Reactions,
Mechanisms and Structure; John Wiley and Sons: New York, 2001.
Inorganic Chemistry, Vol. 44, No. 11, 2005 4099

Esteruelas et al.
distilled. OsH{η5-C5H4(CH2)2NMe2}(PiPr3)2 (1) was prepared ac-
cording to previous report.12 IR spectra were recorded on a Nicolet
550 spectrometer as Nujol mulls on polyethylene sheets. NMR
spectra were recorded on a Varian UNITY 300, a Varian GEMINI
2000-300 MHz, or a Bruker ARX 400 spectrometer. 1H and
13C{1H}, 31P{1H}, and 19F chemical shifts are reported relative to
external tetramethylsilane, H3PO4 (85%), and CFCl3, respectively.
Coupling constants, J, are given in hertz. C, H analyses were carried
out in a Perkin-Elmer 2400 CHNS/O analyzer. FAB mass spectra
analyses were performed with a VG Auto Spec instrument. The
ions were produced with a standard Cs+ gun at 30 kV using
3-nitrobenzyl alcohol (NBA) as the matrix.
Reaction of 1 with HOTf: Formation of [OsH2{η5-C5H4-
(CH2)2NMe2}(PiPr3)2]OTf (2). A solution of 1 (0.20 g, 031 mmol)
in dichloromethane (0.5 mL) was treated with HOTf (27 µL, 0.31
mmol), and the mixture was stirred for 4 h at room temperature.
The solvent was removed, and the solid residue was washed with
pentane (2 × 3 mL) and dried under vacuum to give a white
powder. Yield: 0.18 g (73%). Anal. Calcd for C28H58F3NO3-
OsP2S: C, 42.17; H, 7.27; N, 1.75; S, 4.02. Found: C, 42.32; H,
7.10; N, 1.78; S, 4.37. IR (Nujol, cm-1): ν (Os-H) 2136, 2105
(w), ν (SO3) and ν (CF3) 1270 (br, s), 1148 (s), 1030 (s). MS
(FAB+, m/e): 650 (M+). 1H NMR (400 MHz, CD2Cl2, 293 K): δ
5.37, 5.18 (both m, each 2H, C5H4), 2.58, 2.56 (both m, each 2H,
CH2CH2N), 2.18 (s, 6H, N(CH3)2), 2.05 (m, 6H, PCH), 1.22 (dd,
36H, 3J(HH) ) 6.9, 3J(PH) ) 13.8, PCCH3), -14.19 (t, 2H, 2J(PH)
) 29.1, Os-H). 1H NMR (400 MHz, (CD3)2CO, 293 K): δ 5.77,
5.46 (both m, each 2H, C5H4), 2.73, 2.48 (both m, each 2H,
CH2CH2N), 2.29 (m, 6H, PCH), 2.19 (s, 6H, N(CH3)2), 1.31 (dd,
36H, 3J(HH) ) 7.2, 3J(PH) ) 13.6, PCCH3), -14.09 (t, 2H, 2J(PH)
) 29.2, Os-H). 31P{1H} NMR (161.9 MHz, (CD3)2CO, 293 K):
δ 32.6 (s). 19F NMR (376.3 MHz, (CD3)2CO, 293 K): δ -80 (s).
13C{1H} NMR (100 MHz, (CD3)2CO, 293 K, plus APT): δ 112.2
(-, s, ipso-C5H4), 87.0, 79.2 (+, s, C5H4), 62.9 (-, s, CH2CH2N),
46.5 (+, s, N(CH3)2), 31.9 (+, second-order system, PCH), 28.8
(-, s, CH2CH2N), 20.9 (+, s, PCCH3).
Yield: 0.16 g (65%). The 19F and 1H NMR data were identical to
those reported for 2 with exception of the resonance at -14.09
(t, 1H, 2J(PH) ) 29.2, Os-H). 31P{1H} NMR (161.9 MHz,
(CD3)2CO, 293 K): δ 32.6 (t, 1:1:1, 2J(PD) ) 4.1). 2H NMR (46.05
2
MHz, (CH3)2CO, 293 K): δ -13.8 (t, J(PD) ) 4.1, Os-D).
Reaction of 2 with HOTf: Formation of [OsH2{η5-C5H4-
(CH2)2NHMe2}(PiPr3)2][OTf]2 (3). A suspension of 2 (0.10 g, 0.12
mmol) in dichloromethane (0.5 mL) was treated with HOTf (10
µL, 0.12 mmol), and the resulting colorless mixture was stirred
for 3 h at room temperature. The solvent was removed, and the
solid residue was washed with pentane (2 × 3 mL) and dried under
vacuum to give a white solid. Yield: 0.08 g (70%). Anal. Calcd
for C29H59F6NO6OsP2S2: C, 36.80; H, 6.23; N, 1.48; S, 6.77.
Found: C, 36.81; H, 6.31; N, 1.45; S, 7.00. IR (Nujol, cm-1): ν
(N-H) 3100 (m), ν (Os-H) 2141, 2117 (w), ν (SO3) and ν (CF3)
1270 (br s), 1156 (s), 1031 (s). MS (FAB+, m/e): 800 ([M -
OTf]+), 650 ([M - H]+). 1H NMR (400 MHz, (CD3)2CO, 293 K):
δ 8.77 (br, 1H, NH), 6.07, 5.67 (both m, each 2H, C5H4), 3.68,
3.29 (both m, each 2H, CH2CH2N), 3.21 (s, 6H, N(CH3)2), 2.39
(m, 6H, PCH), 1.42 (dd, 36H, 3J(HH) ) 7.5, 3J(PH) ) 14.4,
2
1
PCCH3), -14.19 (t, 2H, J(PH) ) 28.8, Os-H). H NMR (400
MHz, CD2Cl2, 293 K): δ 8.94 (br, 1H, NH), 5.82, 5.20 (both m,
each 2H, C5H4), 3.44, 2.97 (both m, each 2H, CH2CH2N), 2.95,
2.93 (both s, each 3H, N(CH3)2), 2.12 (m, 6H, PCH), 1.24 (dd,
36H, 3J(HH) ) 7.2, 3J(PH) ) 14.1, PCCH3), -14.19 (t, 2H, 2J(PH)
) 28.8, Os-H). 31P{1H} NMR (161.9 MHz, CD2Cl2, 293 K): δ
31.3 (s). 19F NMR (376.3 MHz, CD2Cl2, 293 K): δ -78.6 (s).
13C{1H} NMR (100 MHz, CD2Cl2, 293 K): δ 122.9 (-, q, 1J(CF)
) 320, CF3), 104.3 (-, s, ipso-C5H4), 85.8, 78.6 (+, s, C5H4), 58.9
(-, s, CH2CH2N), 43.3 (+, s, N(CH3)2), 30.4 (+, second-order
system, PCH), 24.4 (-, s, CH2CH2N), 19.6 (+, s, PCCH3).
Reaction of 2 with DOTf: Formation of [OsH2{η5-C5H4-
(CH2)2NDMe2}(PiPr3)2][OTf]2 (3-Nd1). A procedure analogous to
that described for 3 was followed starting from a solution of 2 (0.10
g, 0.12 mmol) in dichloromethane (0.5 mL) and DOTf (10 µL,
0.12 mmol). Complex 3-Nd1 was obtained as a white powder solid.
1
Yield: 0.08 g (70%). The H, 31P{1H}, and 19F NMR data were
Reaction of 1 with Triethylammonium Tetraphenylborate:
Formation of [OsH2{η5-C5H4(CH2)2NMe2}(PiPr3)2]BPh4 (2-
BPh4). Dichloromethane (2 mL) was added to a mixture of 1 (0.12
g, 0.18 mmol) and triethylammonium tetraphenylborate (0.08 g,
0.18 mmol) at room temperature. The mixture was stirred for 4 h;
the suspension formed was filtered through Celite, and the product
was isolated by precipitation with pentane (1-2 mL) and dried
under vacuum to give a white solid. Yield: 0.13 g (76%). Anal.
Calcd for C51H78BNOsP2: C, 63.27; H, 8.12; N, 1.45. Found: C,
63.15; H, 7.99; N, 1.52. IR (Nujol, cm-1): ν (Os-H) 2139, 2108
identical to those reported for 3 with exception of the absence of
1
2
the resonance at 8.94 ppm in the H NMR spectrum. H NMR
(46.05 MHz, 293 K): (CH3)2CO δ 8.62 (br); CH2Cl2 δ 8.90 (br).
Reaction of 2-d1 with HOTf: Formation of [OsHD{η5-C5H4-
(CH2)2NHMe2}(PiPr3)2][OTf]2 (3-d1). A procedure analogous to
that described for 3 was followed starting from a solution of 2-d1
(0.10 g, 0.12 mmol) in dichloromethane (0.5 mL) and HOTf (10
1
µL, 0.12 mmol). Yield: 0.08 g (70%). The 19F and H NMR data
were identical to those reported for 3 with exception of the
resonance at -14.19 (t, 1H, 2J(PH) ) 28.8, Os-H). 31P{1H} NMR
(161.9 MHz, CD2Cl2, 293 K): δ 31.3 (t (1:1:1), 2J(PD) ) 3.9). 2D
NMR (46.05 MHz, 293 K): (CH3)2CO δ -13.79 (t, 2J(PD) ) 3.9);
1
(w), ν (arC-C) 1580 (m). H NMR (400 MHz, CD2Cl2, 293 K):
δ 7.32, 7.04 (both m, each 8H, BPh4), 6.89 (m, 4H, BPh4), 5.31,
5.11 (both m, each 2H, C5H4), 2.60, 2.42 (both m, each 2H,
CH2CH2N), 2.21 (s, 6H, N(CH3)2), 2.04 (m, 6H, PCH), 1.23 (dd,
36H, 3J(HH) ) 7.2, 3J(PH) ) 13.8, PCCH3), -14.19 (t, 2H, 2J(PH)
) 28.8, Os-H). 31P{1H} NMR (161.9 MHz, (CD3)2CO, 293 K):
δ 32.9 (s). 13C{1H} NMR (100 MHz, CD2Cl2, 293 K + APT): δ
165.4, 164.8, 164.1, 163.5 (-, all s, ipso-C6H5), 136.3, 126.0, 125.9,
125.8, 125.7, 122.0 (+, all s, C6H5), 110.92 (-, s, ipso-C5H4), 84.9,
77.2 (+, both s, C5H4), 61.5 (-, s, CH2CH2N), 45.5 (+, s, N(CH3)2),
30.6 (+, second-order system, PCH), 27.7 (-, s, CH2CH2N), 19.8
(+, s, PCCH3).
Reaction of 1 with DOTf: Formation of [OsHD{η5-C5H4-
(CH2)2NMe2}(PiPr3)2]OTf (2-d1). A procedure analogous to that
described for 2 was followed starting from a solution of 1 (0.20 g,
0.31 mmol) in dichloromethane (0.5 mL) and DOTf (27 µL, 0.31
mmol). Complex 2-d1 was obtained as a white powder solid.
2
CH2Cl2 δ -13.99 (t, J(PD) ) 3.9).
Reaction of 3-d1 with Acetone-d6: Formation of [OsHD{η5-
C5H4(CH2)2NDMe2}(PiPr3)2][OTf]2 (3-d2). A solution of 3-d1 (0.10
g, 0.12 mmol) in acetone-d6 (0.5 mL) was stirred for 6 h at room
temperature. The mixture was evaporated to dryness, and the
resulting white solid was washed twice with pentane (2 × 1 mL).
1
The 19F and H NMR data were identical to those reported for 3
2
with exception of the resonance at -14.19 (t, 1H, J(PH) ) 28.8,
Os-H) and the absence of the one assigned to the NH proton. 31P-
{1H} NMR (161.9 MHz, CD2Cl2, 293 K): δ 31.3 (t (1:1:1), 2J(PD)
2
) 3.9). H NMR (46.05 MHz, CH2Cl2, 293 K): δ 8.90 (br, ND),
2
-13.99 (t, J(PD) ) 3.9).
Reaction of 1 with CH3OTf: Formation of [OsH{η5-C5H4-
(CH2)2NMe3}(PiPr3)2]OTf (4). A solution of 1 (0.25 g, 0.38 mmol)
4100 Inorganic Chemistry, Vol. 44, No. 11, 2005

Hydride-Osmium Complex
2
in toluene (0.5 mL) was treated with CH3OTf (39 µL, 0.34 mmol)
at room temperature, and the reaction mixture was stirred for 12 h.
The solvent was removed under reduced pressure, and the solid
residue was washed with pentane (2 × 3 mL) and dried under
vacuum to give a white solid. Yield: 0.29 g (93%). Anal. Calcd
for C29H60F3NO3OsP2S: C, 42.89; H, 7.45; N, 1.72; S, 3.95.
Found: C, 43.09; H, 7.51; N, 1.89; S, 4.05. IR (Nujol, cm-1): ν
(Os-H) 2052 (m), ν (SO3) and ν (CF3) 1259 (br, s), 1154 (s) and
1031 (s). MS (FAB+, m/e): 813 ([M + H]+). 1H NMR (400 MHz,
CD2Cl2, 293 K): δ 4.80, 4.00 (both m, each 2H, C5H4), 3.73 (m,
2H, CH2CH2N), 3.21 (s, 9H, NCH3), 2.70 (m, 2H, CH2CH2N), 2.01
(m, 6H, PCH), 1.09 (dd, 18H, 3J(HH) ) 7.2, 3J(PH) ) 12.0,
10.1, -31.3 (both d, J(PP′) ) 21). 19F{1H} NMR (376.3 MHz,
(CD3)2CO, 293 K): δ -75.5 (s, CF3).13C{1H} NMR (100 MHz,
(CD3)2CO, 283 K, plus APT plus HETCOR): δ 123.1 (-, q, 1J(CF)
) 331, CF3), 111.4 (-, s, ipso-C5H4), 92.3 (+, d, 2J(PC) ) 5, C5H4),
2
84.3 (+, d, J(PC) ) 6, C5H4), 79.9, 75.8 (+, both s, C5H4), 67.6
1
(-, s, CH2CH2N), 54.7 (+, t(1:1:1), J(NC) ) 4, N(CH3)3), 47.6
(+, d, 1J(PC) ) 36, CH2CHCH3), 36.0 (+, d, 1J(PC) ) 22, PCH),
2
32.4 (+, d, J(PC) ) 27, PCH), 23.8, (-, s, NCH2CH2), 23.4 (+,
d, 2J(PC) ) 6, CH2CHCH3), 22.1, 21.9, (+, both s, PCHCH3), 21.7
2
2
(+, d, J(CP) ) 3, PCHCH3), 21.2 (+, d, J(PC) ) 6, PCHCH3),
20.9 (+, s, PCHCH3), 20.8 (+, d, 2J(PC) ) 5, PCHCH3), 19.0 (+,
2
2
s, PCHCH3), -27.0 (-, dd, J(PC) ) 9, J(P′C) ) 37, Os-CH2).
3
3
Reaction of 1 with CD3OTf: Formation of [OsH{η5-C5H4-
(CH2)2NMe2CD3}(PiPr3)2]OTf (4-d3). A procedure analogous to
that described for 4 was followed starting from a solution of 1 (0.15
g, 0.23 mmol) in toluene (0.5 mL) and CD3OTf (24 µL, 0.22 mmol).
Complex 4-d3 was obtained as a white powder. Yield: 0.16 g (89%).
PCCH3), 1.07 (dd, 18H, J(HH) ) 7.2, J(PH) ) 11.6, PCCH3),
-15.67 (t, 1H, 2J(PH) ) 30.4, Os-H). 1H NMR (400 MHz,
(CD3)2CO, 293 K): δ 4.75, 4.13 (both m, each 2H, C5H4), 3.82
(m, 2H, CH2CH2N), 3.34 (s, 9H, NCH3), 2.89 (m, 2H, CH2CH2N),
2.01 (m, 6H, PCH), 1.13 (dd, 18H, 3J(HH) ) 7.2, 3J(PH) ) 11.6,
3
3
31P{1H}, 19F, and H NMR data were identical to those reported
for 4 with exception of the resonance at 3.34 (s, 6H, N(CH3)2). 2H
NMR (46.05 MHz, (CH3)2CO, 293 K): δ 3.49 (s, CD3).
1
PCCH3), 1.17 (dd, 18H, J(HH) ) 7.2, J(PH) ) 12.0, PCCH3),
-15.68 (t, 1H, 2J(PH) ) 30.6, Os-H). 31P{1H} NMR (161.9 MHz,
(CD3)2CO, 293 K): δ 32.9 (s). 19F NMR (376.3 MHz, (CD3)2CO,
293 K): δ -75.5 (s). 13C{1H} NMR (100 MHz, (CD3)2CO, 293
K, plus HMQC plus APT): δ 88.4 (-, s, ipso-C5H4), 73.3 (+, s,
C5H4), 69.9 (-, s, CH2CH2N), 68.5 (+, second-order system, C5H4),
53.6 (+, t (1:1:1), 1J(NC) ) 4, NMe3), 31.7 (+, second-order
system, PCH), 23.6 (-, s, CH2CH2N), 20.9, 20.8 (+, s, PCCH3).
Reaction of 4-d3 with CH3OTf or CD3OTf: Formation of
[OsH{η5-C5H4(CH2)2NMe2CD3}{CH2CH(CH3)PiPr2}(PiPr3)]-
[OTf]2 (5-d3). A procedure analogous to that described for 5 was
followed starting from a solution of 4-d3 (0.15 g, 0.18 mmol) in
toluene (0.5 mL) and CH3OTf or CD3OTf (20 or 20 µL, respec-
tively, 0.18 mmol). 31P{1H}, 19F, and 1H NMR data were identical
to those reported for 5 with exception of the resonance at 3.40 (s,
Reaction of 4 with CH3OTf: Formation of [OsH{η5-C5H4)-
(CH2)2NMe3}{CH2CH(CH3)PiPr2}(PiPr3)][OTf] (5). A solution
of 4 (0.25 g, 0.31 mmol) in dichloromethane (1 mL) was treated
with CH3OTf (35 µL, 0.31 mmol) at room temperature. The reaction
mixture was stirred for 1 h; the solvent was removed under reduced
pressure, and the solid residue was washed with pentane and dried
under vacuum to produce a white solid. Complex 5 was obtained
as a 1:1 mixture of isomers. Yield: 0.30 g (83%). Anal. Calcd for
2
12H, NMe2 of isomer 5a-d3 and 5b-d3). H NMR (46.05 MHz,
(CH3)2CO, 293 K): δ 3.22 (s, NCD3 of isomers 5a-d3 and 5b-d3).
Reaction of 5 with Acetonitrile: Formation of [Os{η5-C5H4-
(CH2)2NMe3}(NCMe)(PiPr3)2][OTf]2(7) and [Os{η5-C5H4-
(CH2)2NMe3}(NCMe)2(PiPr3)][OTf]2(8). A solution of 5 (0.30
g, 0.31 mmol) in acetonitrile (0.5 mL) was stirred at room
temperature for 12 h. The solvent was removed under reduced
pressure, and the solid residue was washed with pentane (2 × 3
mL) and dried under vacuum to give a light red solid. NMR spectra
of this solid showed the presence of 7 and 8 in a 2:1 molar ratio.
IR (Nujol, cm-1): ν (CtN) 2250 (br), ν (SO3) and ν (CF3) 1270
(br, s), 1148 (s), 1030 (s). MS (FAB+, m/e): 652 ([Os{η5-
C5H4(CH2)2NMe3}(PiPr3)][OTf]). Complex 7. 1H NMR (400 MHz,
CD2Cl2, 293 K, plus COSY plus HMQC): δ 5.13, 4.94 (both m,
each 2H, C5H4), 3.75 (m, 2H, CH2CH2N), 3.25 (s, 9H, NCH3), 2.82
(t, 3H, 5J(PH) ) 1.2, NCCH3), 2.56 (m, 2H, CH2CH2N), 2.48 (m,
6H, PCH), 1.23 (dd, 18H, 3J(HH) ) 6.8, 3J(PH) ) 13.2, PCCH3),
C
29 H59F6NOsO6P2S2: C, 37.45; H, 6.39; N, 1.46; S, 6.67. Found:
C, 37.75; H, 6.22; N, 1.59; S, 6.45. IR (Nujol, cm-1): ν (Os-H)
2053 (w), ν (SO3) and ν (CF3) 1259 (br, s), 1153 (s), 1030 (s). MS
(FAB+, m/e): 330 ([M/2]+), 812 ([M + OTf]+). 5a or 5b isomer.
1H NMR (400 MHz, (CD3)2CO, 293 K, plus H{31P}): δ 6.21,
1
5.90, 5.44, 5.38 (all m, each 1H, C5H4), 3.91 (m, 2H, NCH2CH2),
3.50 (m, 1H, CH2CHCH3), 3.40 (s, 9H, NMe3), 2.90 (m, 2H,
NCH2CH2), 2.56 (m, 3H, PCH), 2.40-2.10 (m, 4H, 2 PCH + Os-
2
CH2), 1.54-1.17 (m, 33H, PCCH3), - 13.96 (dd, 1H, J(P′H) )
26.0, 2J(PH) ) 34.8, Os-H). 31P{1H} NMR (161.9 MHz,
(CD3)2CO, 293 K): δ 11.4, -29.5 (both d, 2J(PP′) ) 26). 19F{1H}
NMR (376.3 MHz, (CD3)2CO, 293 K): δ -75.5 (s, CF3).13C{1H}
NMR (100 MHz, (CD3)2CO, 283 K, plus APT plus HETCOR): δ
1.18 (dd, 18H, J(HH) ) 7.2, J(PH) ) 13.6, PCCH3). 31P{1H}
NMR (161.9 MHz, CD2Cl2, 293 K): δ 0.0 (s). 19F NMR (376.3
MHz, CD2Cl2, 293 K): δ -74.3 (s). 13C{1H} NMR (100 MHz,
CD2Cl2, 293 K, plus HMQC plus APT): δ 123.5 (-, s, ipso-C5H4),
3
3
1
123.1 (-, q, J(CF) ) 331, CF3), 108.7 (-, s, ipso-C5H4), 90.7
2
2
(+, d, J(PC) ) 4, C5H4), 85.0 (+, d, J(PC) ) 6, C5H4), 81.2,
77.2 (+, both s, C5H4), 67.8 (-, s, CH2CH2N), 54.7 (+, t(1:1:1),
1J(NC) ) 4, N(CH3)3), 49.9 (+, d, 1J(PC) ) 35, CH2CHCH3), 36.2
1
121.0 (-, q, J(FC) ) 321, CF3SO3), 96.0 (-, br, NtC), 73.1,
69.0 (+, s, C5H4), 66.3 (-, s, CH2CH2N), 53.8 (+, t(1:1:1), 1J(NC)
) 4, NMe3), 30.0 (+, second-order system, PCH), 21.0 (-, s,
CH2CH2N), 20.7, 20.6 (+, both s, PCCH3), 5.2 (+, s, NtCCH3).
Complex 8. 1H NMR (400 MHz, CD2Cl2, 293 K, plus COSY plus
HMQC): δ 4.94, 4.57 (both m, each 2H, C5H4), 3.66 (m, 2H,
CH2CH2N), 3.26 (s, 9H, NCH3), 2.81 (m, 2H, CH2CH2N), 2.66 (d,
1
1
(+, d, J(PC) ) 22, PCH), 31.5 (+, d, J(PC) ) 28, PCH), 28.1
1
2
(+, d, J(PC) ) 20, PCH), 26.1 (+, d, J(PC) ) 6, CH2CHCH3),
23.5 (+, s, CH2CH2N), 22.2, 22.1, 22.0, 21.8 (+, all s, PCHCH3),
21.7 (+, d, 2J(CP) ) 3, PCHCH3), 21.4 (+, d, 2J(PC) ) 5,
PCHCH3), 19.9 (+, s, PCHCH3), -27.1 (-, dd, 2J(PC) ) 9, 2J(P′C)
) 36, Os-CH2). 5a or 5b isomer. 1H NMR (400 MHz, (CD3)2CO,
293 K, plus 1H{31P}): δ 5.95, 5.74, 5.73, 5.26 (all m, each
1H, C5H4), 3.91 (m, 2H, NCH2CH2), 3.40 (s, 9H, NMe3), 3.19 (m,
1H, CH2CHMe), 2.97 (m, 2H, NCH2CH2), 2.90-2.70 (m, 2H,
Os-CH2), 2.56 (m, 3H, PCH), 2.40-2.10 (m, 2H, PCH), 1.54-
5
6H, J(PH) ) 1.2, NCCH3), 2.37 (m, 3H, PCH), 1.23 (dd, 9H,
3J(HH) ) 6, 3J(PH) ) 12.4, PCCH3). 31P{1H} NMR (161.9 MHz,
CD2Cl2, 293 K): δ 17.5 (s). 19F NMR (376.3 MHz, CD2Cl2, 293
K): δ -74.3 (s). 13C{1H} NMR (100.57 MHz, CD2Cl2, 293 K,
plus HMQC plus APT): δ 124.6 (-, s, ipso-C5H4), 121.0 (-, q,
2
2
3
1.17 (m, 33H, PCCH3), - 13.70 (dd, 1H, J(P′H) ) 28.8, J(PH)
1J(FC) ) 321, CF3SO3), 88.7 (-, d, J(PC) ) 7.0, NtC), 72.5,
) 36.8, Os-H). 31P{1H} NMR (161.9 MHz, (CD3)2CO, 293 K): δ
67.5 (+, s, C5H4), 66.3 (-, s, CH2CH2N), 53.6 (+, t(1:1:1), 1J(NC)
Inorganic Chemistry, Vol. 44, No. 11, 2005 4101

Esteruelas et al.
1
Table 2. Crystal Data and Data Collection and Refinement for 4
) 3, NMe3), 27.1 (+, d, J(PC) ) 26, PCH), 21.0 (-, s, CH2-
CH2N), 19.6 (+, s, PCCH3), 4.5 (+, s, NtCCH3).
Crystal Data
Reaction of 4 with Methanol: Formation of [OsH2(η5-
C5H4CHdCH2)(PiPr3)2]OTf (9). A solution of 4 (0.15 g, 0.15
mmol) in methanol was stirred at room temperature for 24 h. The
resulting colorless solution was evaporated to dryness, and the
product was extracted with dichloromethane, filtered through Celite/
alumina (9:1), and washed twice with pentane to yield a white solid.
Yield: 9.6 × 10-2 g (63%). Anal. Calcd for C26H51F3OsO3P2S:
C, 41.47; H, 6.83; S, 4.26. Found C, 41.56; H, 6.82; S, 4.12. IR
(Nujol, cm-1): ν (Os-H) 2145, 2111, ν (CdC) 1633, ν (SO3) and
ν (CF3) 1270 (br, s), 1148 (s), 1030 (s). MS (FAB+, m/e): 605
(M+). 1H NMR (400 MHz, CD2Cl2, 293 K, plus 1H{31P} plus
formula
mol wt
color and habit
symmetry, space group
a, Å
b, Å
c, Å
C29H60F3NO3OsP2S
811.98
colorless, irregular block
triclinic, P1h
8.5873(4)
10.3482(5)
20.1959(10)
77.9920(10)
83.5540(10)
83.3500(10)
1736.39(14)
2
R, deg
â, deg
γ, deg
V, Å3
Z
D
calc, g cm-3
1.553
Data Collection and Refinement
Bruker Smart APEX
3
3
COSY): δ 6.40 (dd, 1H, J(HHcis) ) 10.8, J(HHtrans) ) 17.6,
-CHd), 5.64 (d, 1H, 3J(HHtrans) ) 17.6, CdCHtrans), 5.55 (m, 2H,
C5H4), 5.43 (d, 1H, 3J(HHcis) ) 10.8, CdCHcis), 5.30 (m, 2H, C5H4),
2.10 (m, 6H, PCH), 1.23 (dd, 36H, 3J(HH) ) 6.8, 3J(PH) ) 14.0,
diffractometer
λ(Mo KR), Å
monochromator
scan type
0.71073
graphite oriented
ω scans
3.869
3, 57
100
21900
8307 (Rint ) 0.0323)
380/0
µ, mm-1
2
PCCH3), -14.22 (t, 2H, J(PH) ) 29.2, Os-H). 31P{1H} NMR
2θ, range deg
(161.9 MHz, CD2Cl2, 293 K): δ 32.2 (s). 19F NMR (376.3 MHz,
CD2Cl2, 293 K): δ -78.8 (s) 13C{1H} NMR (100 MHz, CD2Cl2,
293 K, plus HMQC plus APT): δ 127.3 (+, s, -CHd), 120.5 (-,
s, dCH2), 107.6 (-, s, ipso-C5H4), 82.3, 78.4 (+, both s, C5H4),
30.6 (+, second-order system, PCH), 19.7 (+, s, PCCH3).
temp, K
no. of data collected
no. of unique data
no. of params/restraints
R1a [F2 > 2σ(F2)]
R2b (all data)
0.0261
0.0451
0.842
Sc (all data)
Reaction of 4 with Methanol-d4: Formation of [OsHD(η5-
C5H4CHdCH2)(PiPr3)2]OTf (9-d1). A procedure analogous to that
described for 9 was followed starting from a solution of 4 in
methanol-d4. Complex 9-d1 was obtained as a white solid. 1H NMR
data were identical to those reported for 9 with exception of the
resonance at -14.22 (t, 1H, 2J(PH) ) 29.2, Os-H). 31P{1H} NMR
a R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. b R2(F2) ) {∑[w(Fo - Fc )2]/
2
2
2
2
2
∑[w(Fo )2]}1/2 c GOF ) S ) {∑[Fo - Fc )2]/(n - p)}1/2 where n is the
.
number of reflections and p is the number of refined parameters.
the white precipitate by filtration through Celite, evaporated to
dryness, and dried under vacuum to yield a yellow powder. Yield:
0.10 g (64%). Anal. Calcd for C25H50OsP2: C, 49.81; H, 8.36.
Found: C, 50.04; H, 8.43. IR (Nujol, cm-1): ν (Os-H) 2083, ν
2
2
(161.9 MHz, CD2Cl2, 293 K): δ 32.2 (t, J(PD) ) 4). H NMR
2
(46.05 MHz, CH2Cl2, 293 K): δ -14.13 (t, J(PD) ) 4, Os-D).
Reaction of 4 with HOTf: Formation of [OsH2{η5-C5H4-
(CH2)2NMe3}(PiPr3)2][OTf]2(10). A solution of 4 (0.25 g, 0.31
mmol) in dichloromethane (0.5 mL) was treated with HOTf (27
µL, 0.31 mmol) at room temperature, and the reaction mixture
was stirred for 1 h. The solvent was removed under reduced
pressure, and the solid residue was washed with pentane (2 × 3
mL) and dried under vacuum to give a white solid. Yield: 0.27 g
(90%). Anal. Calcd for C30H61F6NOsO6P2S2: C, 37.45; H, 6.39;
N, 1.46; S, 6.67. Found C, 37.31; H, 5.98; N, 1.40; S, 6.98. IR
(Nujol, cm-1): ν (Os-H) 2044, 2020 (w), ν (SO3) and ν (CF3)
1270 (br, s), 1148 (s), 1030 (s). MS (FAB+, m/e): 814 ([M -
(CdC) 1615. MS (FAB+, m/e): 605 ([M + H]+). H NMR (400
1
MHz, C6D6, 293 K, plus H{31P} plus COSY): δ 6.55 (dd, 1H,
1
3J(HHcis) ) 10.8, 3J(HHtrans) ) 17.2, dCH), 5.22 (d, 1H, 3J(HHtrans
)
) 17.2, dCHHtrans), 5.00 (d, 1H, 3J(HHcis) ) 10.8, dCHHcis), 4.64,
4.52 (both m, each 2H, C5H4), 1.94 (m, 6H, PCH), 1.12 (dd, 18H,
3J(HH) ) 7.2, J(PH) ) 12.4, PCCH3), 1.15 (dd, 18H, J(HH) )
7.2, 3J(PH) ) 12.4, PCCH3), -16.67 (t, 2H, 2J(PH) ) 31.6,
Os-H). 31P{1H} NMR (161.9 MHz, C6D6, 293 K): δ 27.7 (s).
13C{1H} NMR (100 MHz, C6D6, 293 K, plus HMQC plus APT):
δ 134.5 (+, s, dCH), 107.9 (-, s, dCH2), 87.9 (-, s, ipso-C5H4),
72.8, 69.3 (+, both s, C5H4), 31.1 (+, d, 1J(PC) ) 24, PCH), 21.1,
20.6 (+, both s, PCCH3). The same procedure was followed in all
of the reported deprotonation reactions starting from the corre-
sponding osmium derivatives, 3-Nd1 (0.15 g, 0.16 mmol), 3-d1 (0.15
g, 0.16 mmol), or 10 (0.30 g, 0.31 mmol) and sodium methoxide
(8.6 × 10-3 g, 0.16 mmol (3-Nd1), 8.6 × 10-3 g, 0.16 mmol
(3-d1), or 18 × 10-3 g, 0.34 mmol (10), respectively. 1H, 31P{1H},
and 19F NMR spectra of the corresponding solids were identical to
those reported for 2, 2-d1, and 9, respectively.
3
3
1
OTf]+). H NMR (400 MHz, CD2Cl2, 293 K): δ 5.99, 5.22 (both
m, each 2H, C5H4), 3.73 (m, 2H, CH2CH2N), 3.23 (s, 9H, NCH3),
2.97 (m, 2H, CH2CH2N), 2.15 (m, 6H, PCH), 1.24 (dd, 36H, 3J(HH)
3
2
) 7.2, J(PH) ) 14.1, PCCH3), -14.22 (t, 2H, J(PH) ) 29.1,
Os-H). 1H NMR (400 MHz, (CD3)2CO, 293 K): δ 6.02, 5.54 (both
m, each 2H, C5H4), 3.84 (m, 2H, CH2CH2N), 3.38 (s, 9H, NCH3),
3.30 (m, 2H, CH2CH2N), 2.30 (m, 6H, PCH), 1.31 (dd, 36H, 3J(HH)
3
2
) 7.2, J(PH) ) 14.0, PCCH3), -14.09 (t, 2H, J(PH) ) 29.2,
Os-H). 31P{1H} NMR (161.9 MHz, (CD3)2CO, 293 K): δ 32.8
(s). 19F NMR (376.3 MHz, (CD3)2CO, 293 K): δ -74.3 (s). 13C-
{1H} NMR (100 MHz, (CD3)2CO, 293 K, plus HMQC plus APT):
δ 106.0 (-, s, ipso-C5H4), 87.9, 80.7 (+, s, C5H4), 68.7 (-, s,
CH2CH2N), 54.8 (+, t(1:1:1), 1J(NC) ) 4, NMe3), 32.0 (+, second-
order system, PCH), 24.8 (-, s, CH2CH2N), 20.9 (+, s, PCCH3).
Reaction of 9 with Sodium Methoxide: Formation of OsH-
(η5-C5H4CHdCH2)(PiPr3)2 (11). Tetrahydrofurane (2 mL) was
added to a mixture of complex 9 (0.25 g, 0.33 mmol) and sodium
methoxide (19 × 10-3 g, 0.36 mmol) at room temperature, and the
reaction mixture was stirred for 24 h. The solvent was removed
under reduced pressure, and the solid residue was extracted with
pentane (2 × 2 mL). The pale yellow solution was separated from
X-ray Analysis of 4. An irregular crystal of 0.20 × 0.12 × 0.08
mm was mounted on a Bruker Smart APEX CCD diffractometer,
equipped with a normal focus and a 2.4 kW sealed tube source
(molybdenum radiation, λ ) 0.71073 Å) operating at 50 kV and
40 mA, at 100.0(2) K. Data were collected over the complete sphere
by a combination of four sets. Each frame exposure time was 10 s
covering 0.3° in ω. The cell parameters were determined and refined
by the least-squares fit of 7645 collected reflections. The first 100
frames were collected at the end of the data collection to monitor
crystal decay. The absorption correction was performed with the
SADABS program which is based on the Blessing method.23
Lorentz and polarization corrections were also performed. The
structure was solved by Patterson and Fourier methods and refined
4102 Inorganic Chemistry, Vol. 44, No. 11, 2005

Hydride-Osmium Complex
by full matrix least-squares using the Bruker SHELXTL program
package24 minimizing w(Fo2 - Fc2)2. The hydride was refined as a
free isotropic atom. The weighted R factors (R2) and goodness of
fit (S) are based on F2, and the conventional R factors are based on
F. Crystal data and details of the data collection and refinement
are given in Table 2.
Acknowledgment. Financial support from the MCYT of
Spain (Projects BQU2002-00606) is acknowledged.
Supporting Information Available: Tables of crystallographic
data and bond lengths and angles. This material is available free
of charge via the Internet at http://pubs.acs.org.
(23) Blessing, R. H. Acta Crystallogr., Sect. A. 1995, 51, 33.
(24) SHELXTL Package, version 6.1; Bruker-AXS: Madison, WI, 2000.
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