Efficient concatenation of C=C reduction, C-H bond activation, and C-C and C-N coupling reactions on osmium: Assembly of two allylamines and an allene

Article abstract of DOI:10.1021/om100715k

An osmium-promoted assembly of two allylamine molecules and gem-disubstituted allenes to afford π-allyl ligands with a diamine pendant substituent is reported. Complex OsH₂Cl₂(P ⁱPr₃)₂ (1) reacts with 2 equiv of allylamine to give Os(CH₂CH₂CH₂NH₂) Cl(η²-CH₂=CHCH₂NH₂)(P ⁱPr₃) (2). At 0 °C carbon monoxide displaces the chloride ligand of 2. At 50 °C, the resulting salt [Os(CH₂CH ₂CH₂NH₂)(CO)(η²-CH ₂=CHCH₂NH₂)(PⁱPr₃)]Cl (3) is transformed into Os(CH=CHCH₂NH₂)Cl(CO)( ⁿPrNH₂)(PⁱPr₃) (4) by an intramolecular σ-bond metathesis between the alkyl and olefin donor units of 3. The addition of HBF₄ to the diethyl ether solutions of 4 affords the alkylidene [OsCl(=CHCH₂CH₂NH ₂)(CO)(ⁿPrNH₂)(PⁱPr ₃)]BF₄ (5). The reaction of 4 with TlPF₆ under CO atmosphere leads to the cis-dicarbonyl derivative [Os(CH=CHCH ₂NH₂)(CO)₂(ⁿPrNH₂)(P ⁱPr₃)]PF₆ (6), which by treatment with 1-methyl-1-(trimethylsilyl)allene and 1,1-dimethylallene affords [Os{η³-CH₂C(CHMeR)CHCH(NHⁿPr)CH ₂NH₂}(CO)₂(PⁱPr₃)]PF ₆ (R = SiMe₃ (7) Me (8)), as a result of the insertion of the allene into the Os-C(sp²) bond of 6 and the subsequent regio- and stereoselective 1,4-addition of a N-H bond of ⁿPrNH₂ to the resulting olefin-allyl organic fragment. In agreement with this, under CO atmosphere, complex 4 affords Os(CH=CHCH₂NH₂)Cl(CO) ₂(PⁱPr₃) (9), which reacts with 1-methyl-1-(trimethylsilyl)allene in the presence of TlPF₆ to give [Os{η³-CH₂C(CH=CHCH₂NH₂) C(SiMe₃)CH₃}(CO)₂(PⁱPr ₃)]PF₆ (10). The addition of ⁿPrNH₂ and PhNH₂ to 10 leads to 7 and [Os{η³-CH ₂C[CHMe(SiMe₃)]CHCH(NHPh)CH₂NH ₂}(CO)₂(PⁱPr₃)]PF₆ (11), respectively. The X-ray structures of 2, 4, 7, and 10 are also reported.

Full text of DOI:10.1021/om100715k

6298 Organometallics 2010, 29, 6298–6307
DOI: 10.1021/om100715k
Efficient Concatenation of CdC Reduction, C-H Bond Activation, and
C-C and C-N Coupling Reactions on Osmium: Assembly of Two
Allylamines and an Allene
~
Miguel Baya,* Miguel A. Esteruelas,* and Enrique Onate
´
ꢀ
Departamento de Quımica Inorganica, Instituto de Ciencia de Materiales de Aragon,
ꢀ
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received July 21, 2010
An osmium-promoted assembly of two allylamine molecules and gem-disubstituted allenes
to afford π-allyl ligands with a diamine pendant substituent is reported. Complex OsH2Cl2(PiPr3)2
(1) reacts with 2 equiv of allylamine to give Os(CH2CH2CH2NH2)Cl(η2-CH2dCHCH2NH2)-
jj
j
(PiPr3) (2). At 0 °C carbon monoxide displaces the chloride ligand of 2. At 50 °C, the
resulting salt [Os(CH2CH2CH2NH2)(CO)(η2-CH2dCHCH2NH2)(PiPr3)]Cl (3) is transformed into
jj
j
Os(CHdCHCH2NH2)Cl(CO)(nPrNH2)(PiPr3) (4) by an intramolecular σ-bond metathesis
between the alkyl and olefin donor units of 3. The addition of HBF4 to the diethyl ether solutions
of 4 affords the alkylidene [OsCl(dCHCH2CH2NH2)(CO)(nPrNH2)(PiPr3)]BF4 (5). The reaction of
4 with TlPF6 under CO atmosphere leads to the cis-dicarbonyl derivative [Os(CHdCHCH2NH2)-
(CO)2(nPrNH2)(PiPr3)]PF6 (6), which by treatment with 1-methyl-1-(trimethylsilyl)allene and
1,1-dimethylallene
affords
[Os{η3-CH2C(CHMeR)CHCH(NHnPr)CH2NH2}(CO)2(PiPr3)]-
PF6 (R = SiMe3 (7) Me (8)), as a result of the insertion of the allene into the Os-C(sp2) bond
of 6 and the subsequent regio- and stereoselective 1,4-addition of a N-H bond of nPrNH2
to the resulting olefin-allyl organic fragment. In agreement with this, under CO atmosphere,
complex 4 affords Os(CHdCHCH2NH2)Cl(CO)2(PiPr3) (9), which reacts with 1-methyl-
1-(trimethylsilyl)allene in the presence of TlPF6 to give [Os{η3-CH2C(CHdCHCH2NH2)-
C(SiMe3)CH3}(CO)2(PiPr3)]PF6 (10). The addition of nPrNH2 and PhNH2 to 10 leads to 7
and [Os{η3-CH2C[CHMe(SiMe3)]CHCH(NHPh)CH2NH2}(CO)2(PiPr3)]PF6 (11), respectively.
The X-ray structures of 2, 4, 7, and 10 are also reported.
Introduction
elemental processes, in particular C-H bond activation2
and C-C3 and C-heteroatom4 coupling reactions.
The design of novel metal-mediated synthesis of functio-
nalized organic fragments from basic hydrocarbon units is
one of the tasks of chemical science.1 The assembly of
organic moieties, in the manner like a child plays with a
LEGO, has become a fascinating challenge. This aim re-
quires not only the entry in a consecutive and controlled way
of organic molecules into a coordination transition-metal
complex but also the efficient concatenation of different
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*Corresponding authors. E-mail: miguelbayamoscu@yahoo.es;
maester@unizar.es.
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pubs.acs.org/Organometallics
Published on Web 11/10/2010
2010 American Chemical Society

Article
The iPr3P-Os-PiPr3 metal fragment leaves available the
Organometallics, Vol. 29, No. 23, 2010 6299
unsaturated organic fragments,10 is a target of great interest.
Allenes are a unique class of 1,2-dienes, which have shown a
versatile reactivity. Today, the allene unit is an established
member of the tools utilized in modern organic synthetic
chemistry, in particular for reactions catalyzed by transition
metals.11 The coordination of one of the carbon-carbon
double bonds to the metal center produces the activation of
the allene, which can then undergo several reactions includ-
ing C-C coupling12 and N-H additions.13
In the search for novel procedures that are efficient in the
synthesis of new organic fragments, we have studied the
assembly of allylamine and gem-disubstituted allenes pro-
moted by the complex OsH2Cl2(PiPr3)2. In this paper we
show an unprecedent joining of two allylamine molecules
and an allene substrate involving the efficient concatenation
of four reactions: hydrometalation,14 intramolecular σ-bond
metathesis between alkyl and alkenyl groups,15 alkenyl-
allene coupling, and N-H addition to a conjugated olefin-
allyl system.
region in the perpendicular plane to the P-Os-P direction for
the entry of ligands.5 By using this metal fragment, we have
previously assembled (Chart 1) alkynyl, alkenyl, and carbyne
ligands to afford an isometallabenzene with the structure of a
1,2,4-cyclohexatriene6 (I) and an allenylidene ligand, an alke-
nyl group, and an acetonitrile molecule to form osmacyclo-
pentapyrroles7 (II). Furthermore, as a part of our work on the
chemistry of the complex OsH2Cl2(PiPr3)2,8 we have also
shown that this compound assembles two 2-vinylpyridine and
two acetylene molecules to give the ligand py-C8H-C7H-
C6H-C5H{-C4H-C3HdC2H-C1H}-py, which coordi-
nates to the [Os(PiPr3)]þ metal fragment by the nitrogen atoms
of both pyridine rings, the C8H-C7H-C6H unit in an η3-allyl
manner, and C1 to form a carbene (III). Its formation is a
one-pot synthesis of multiple complex reactions. In addition
to a 1,3-hydrogen shift, three selective C-C couplings are
efficiently concatenated.9
Nitrogen is present in many compounds of enormous
practical importance, ranging from pharmaceutical agents
and biological probes to electroactive materials. Thus, the
development of novel synthetic methods, including direct
formation of new C-N bonds by addition of an amine to
Results and Discussion
1. Reaction of OsH2Cl2(PiPr3)2 with Allylamine: Coordi-
nation and Hydrometalation of C-C Double Bonds.
Treatment for 20 h at 20 °C of complex OsH2Cl2(PiPr3)2
(1) in toluene with 4.2 equiv of allylamine gives rise
to the release of [HPiPr3]Cl and the formation of
(5) Esteruelas, M. A.; Oro, L. A. Adv. Organomet. Chem. 2001, 47, 1.
~
(6) Barrio, P.; Esteruelas, M. A.; Onate, E. J. Am. Chem. Soc. 2004,
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(7) Bolano, T.; Castarlenas, R.; Esteruelas, M. A.; Onate, E. J. Am.
~
~
Os(CH2CH2CH2NH2)Cl(η2-CH2dCHCH2NH2)(PiPr3) (2),
Chem. Soc. 2006, 128, 3965.
(8) For recent papers see: (a) Esteruelas, M. A.; Lopez, A. M.; Onate,
jj
j
ꢀ
~
which is isolated as a yellow solid in 65% yield, according
to eq 1.
ꢀ
E.; Royo, E. Organometallics 2004, 23, 3021. (b) Esteruelas, M. A.; Lopez,
~
A. M.; Onate, E.; Royo, E. Organometallics 2004, 23, 5633. (c) Esteruelas,
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M. A.; Fernandez-Alvarez, F. J.; Onate, E. J. Am. Chem. Soc. 2006, 128,
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13044. (d) Esteruelas, M. A.; Fernandez-Alvarez, F. J.; Onate, E. Organo-
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metallics 2007, 26, 5239. (e) Esteruelas, M. A.; Masamunt, A. B.; Olivan, M.;
~
Onate, E.; Valencia, M. J. Am. Chem. Soc. 2008, 130, 11612. (f) Esteruelas,
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M. A.; Fernandez-Alvarez, F. J.; Onate, E. Organometallics 2008, 27, 6236.
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(g) Esteruelas, M. A.; Fuertes, S.; Olivan, M.; Onate, E. Organometallics
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2009, 28, 1582. (h) Buil, M. L.; Esteruelas, M. A.; Garces, K.; Onate, E.
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Organometallics 2009, 28, 5691. (i) Esteruelas, M. A.; Fernandez-Alvarez,
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~
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F. J.; Lopez, A. M.; Mora, M.; Onate, E. J. Am. Chem. Soc. 2010, 132, 5600.
ꢀ
(9) Esteruelas, M. A.; Fernandez-Alvarez, F. J.; Olivan, M.; Onate,
~
Complex 2 has incorporated two substrate molecules.
One of them coordinates the nitrogen atom to the metal
center and inserts the C-C double bond of the allyl
group into an Os-H bond, whereas the other one is coordi-
nated to the metal center by the nitrogen atom and the
C-C double bond. The reaction of 1 with allylamine con-
trasts with that of 1 with vinylpyridine, which leads to
E. J. Am. Chem. Soc. 2006, 128, 4596.
€
(10) Muller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M.
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Os(CHdCH-C5H5N)Cl(η2-CH2dCH-C5H5N)(PiPr3).9 Al-
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jj
j
though this compound has also incorporated two substrate
molecules, the loss of molecular hydrogen during the reaction
prevents the insertion into an Os-H bond of the C-C double
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ꢀ
See for example: (a) Chaloner, P. A.; Esteruelas, M. A.; Joo, F.; Oro,
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~
Olivan, M.; Onate, E. Organometallics 2006, 25, 3076. (b) Lin, Z. Coord.
Chem. Rev. 2007, 251, 2280.

6300 Organometallics, Vol. 29, No. 23, 2010
Baya et al.
Chart 1
Figure 1. Thermal ellipsoid drawing of one of the two indepen-
dent molecules of complex 2, with ellipsoids at 50% probability.
Some hydrogen atoms have been omitted for clarity. Selected
bond of the vinyl substituent of one of the heterocycles.
Instead of the latter, a vinyl C-H bond activation occurs9
in addition to the [HPiPr3]Cl release.
˚
bond lengths (A) and angles (deg): Os(1)-N(1) 2.184(6), 2.171(6);
Os(1)-N(2) 2.173(6), 2.173(6); Os(1)-C(2) 2.076(7), 2.153(7);
Os(1)-C(3) 2.143(7), 2.143(7); Os(1)-C(6) 2.122(7), 2.117(7);
C(2)-C(3) 1.390(10), 1.395(10); C(5)-C(6) 1.527(10), 1.544(11);
P(1)-Os(1)-N(1) 168.51(16), 169.97(17); C(6)-Os(1)-N(2)
79.0(2), 79.3(3); C(6)-Os(1)-Cl(1) 154.99(19), 155.7(2).
Complex 2 has been characterized by X-ray diffraction
analysis. Its structure has two chemically equivalent but crys-
tallographically independent molecules of the complex in
the asymmetric unit. A drawing of one of them is shown in
Figure 1. The coordination around the osmium atom can be
rationalized as a distorted octahedron with the phosphorus
atom of the phosphine ligand trans disposed to the nitrogen
atom of the coordinated allylamine (P(1)-Os(1)-N(1) =
168.51(16)° and 169.97(17)°). The perpendicular plane is
formed by the inserted group, which acts with bite angles
C(6)-Os(1)-N(2) of 79.0(2)° and 79.3(3)°, the chloride ligand
trans disposed to C(6) (Cl(1)-Os(1)-C(6)=154.99(19)° and
155.7(2)°) and the coordinated C(2)-C(3) double bond
trans disposed to N(2). The Os-C(6) bond lengths of
˚
lengths C(2)-C(3) of 1.390(10) and 1.395(10) A, suggests a
strong osmium-olefin interaction.
The 13C{1H} NMR spectrum of 2 is consistent with the
structure shown in Figure 1. In agreement with the presence
of an Os-C(sp3) bond in the complex, the spectrum contains
at 5.9 ppm a doublet with a C-P coupling constant of 3.5 Hz,
corresponding to C(6). The C(sp2) resonances due to C(2)
and C(3) are observed at 29.3 and 35.5 ppm, respectively. The
first of them appears as a singlet, whereas the second one is a
doublet with a C-P coupling constant of 2.6 Hz. The 31P-
{1H} NMR spectrum shows a singlet at -7.3 ppm.
˚
2.122(7) and 2.117(7) A lie on the lower part of the range
reported for the limited number of Os-C(sp3) complexes
2. σ-Hydrogen Migration from the Coordinated to the
Inserted C-C Double Bond. Carbon monoxide dis-
places the chloride ligand of 2 from the coordination
sphere of the metal center. Thus, the stirring at 0 °C
of toluene solutions of this compound under atmo-
spheric carbon monoxide pressure affords the salt
16
˚
characterized by X-ray diffraction analysis (2.15-2.21 A),
˚
whereas the distances Os-C(2) of 2.076(7) and 2.153(7) A
˚
and Os-C(3) of 2.143(7) A lie on the lower part of the range
reported for metal-olefin distances in osmium-olefin com-
17
˚
pounds (2.13-2.28 A) and are statistically identical with
the Os-C(6) bond lengths. This, along with the olefinic bond
[Os(CH2CH2CH2NH2)(CO)(η2-CH2dCHCH2NH2)(PiPr3)]Cl
jj
j
(16) (a) Lindner, E.; Jansen, R.-M.; Hiller, W.; Fawzi, R. Chem. Ber.
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J. Organomet. Chem. 1990, 383, 481. (c) Esteruelas, M. A.; Lahoz, F. J.;
(3), which is isolated as a white solid in 84% yield, according to
Scheme 1. The presence of a carbonyl ligand in the cation of 3
is strongly supported by its IR and 13C{1H} NMR spectrum.
The IR shows a ν(CO) absorption at 1945 cm-1, whereas the
13C{1H} NMR spectrum contains a carbonyl resonance at
187.0 ppm as a doublet with a C-P coupling constant of 14.1
Hz. As a consequence of the reduction of the electron density
of the metal center, the Os-C(sp3) (δ 26.7) and C(sp2) (δ 39.9
and 42.1) resonances of 3 are shifted toward lower field (about
21 and 11 and 7 ppm, respectively) with regard to those of 2. The
same phenomenon occurs in the 31P{1H} NMR spectrum,
which contains a singlet at -0.2 ppm, i.e., shifted 7 ppm toward
lower field with regard to that of 2.
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Lopez, J. A.; Oro, L. A.; Schl€unken, C.; Valero, C.; Werner, H. Organome-
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Zanazzi, P. Inorg. Chem. 1993, 32, 547. (e) Esteruelas, M. A.; Gonzalez,
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A. I.; Lopez, A. M.; Onate, E. Organometallics 2003, 22, 414. (f) Esteruelas,
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M. A.; Lopez, A. M.; Onate, E.; Royo, E. Organometallics 2005, 24, 5780.
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(g) Esteruelas, M. A.; García-Yebra, C.; Olivan, M.; Onate, E.; Valencia, M.
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Eisenstein, O.; Huffman, J. C.; Caulton, K. G. Inorg. Chem. 1994, 33,
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4966. (b) Edwards, A. J.; Esteruelas, M. A.; Lahoz, F. J.; Lopez, A. M.; Onate,
E.; Oro, L. A.; Tolosa, J. I. Organometallics 1997, 16, 1316. (c) Edwards,
A. J.; Elipe, S.; Esteruelas, M. A.; Lahoz, F. J.; Oro, L. A.; Valero, C.
Organometallics 1997, 16, 3828. (d) Buil, M. L.; Esteruelas, M. A.; García-
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Yebra, C.; Gutierrez-Puebla, E.; Olivan, M. Organometallics 2000, 19, 2184.
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(e) Esteruelas, M. A.; García-Yebra, C.; Olivan, M.; Onate, E. Organome-
The electron density on the metal center of 3 does not
appear to be enough for stabilizing the coordination of two
π-acidic ligands, the carbonyl group and the C-C double
bond, to the osmium atom. Thus, the salt is moderately
stable in dichloromethane. At 50 °C it is converted to give
~
tallics 2000, 19, 3260. (f) Baya, M.; Esteruelas, M. A.; Onate, E. Organo-
~
metallics 2002, 21, 5681. (g) Barrio, P.; Esteruelas, M. A.; Onate, E.
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M. A.; Onate, E. Organometallics 2004, 23, 1416. (i) Barrio, P.; Esteruelas,
M. A.; Onate, E. Organometallics 2004, 23, 3627. (j) Baya, M.; Buil, M. L.;
Esteruelas, M. A.; Onate, E. Organometallics 2005, 24, 2030. (k) Esteruelas,
M. A.; García-Yebra, C.; Olivan, M.; Onate, E. Inorg. Chem. 2006, 45,
~
~
~
ꢀ
~
ꢀ
ꢀ
ꢀ
10162. (l) Esteruelas, M. A.; Hernandez, Y. A.; Lopez, A. M.; Olivan, M.;
after 8 h the neutral compound Os(CHdCHCH2NH2)Cl-
(CO)(nPrNH2)(PiPr3) (4) in quantitative yield (Scheme 1). Its
formation involves an R-hydrogen migration from the ter-
minal olefinic CH2 group of the coordinated allylamine to
Rubio, L. Organometallics 2008, 27, 799. (m) Esteruelas, M. A.; García-
Yebra, C.; Onate, E. Organometallics 2008, 27, 3029. (n) Castro-Rodrigo,
R.; Esteruelas, M. A.; Lopez, A. M.; Lopez, F.; Mascarenas, J. L.; Olivan, M.;
Onate, E.; Saya, L.; Villarino, L. J. Am. Chem. Soc. 2010, 132, 454.
~
ꢀ
ꢀ
~
ꢀ
~
~

Article
Organometallics, Vol. 29, No. 23, 2010 6301
Scheme 1
Figure 2. Thermal ellipsoid drawing of 4, with ellipsoids at
50% probability. Some hydrogen atoms have been omitted for
˚
clarity. Selected bond lengths (A) and angles (deg): Os-N(1)
2.217(3); Os-N(2) 2.178(2); Os-C(3) 2.040(3); C(2)-C(3)
1.343(4); C(5)-C(6) 1.520(4); P-Os-N(2) 176.43(7); N(1)-
Os-C(3) 78.31(11); N(1)-Os-C(7) 171.49(11); Cl-Os-C(3)
160.32(9); Os-C(2)-C(3) 118.3(2); C(1)-C(2)-C(3) 120.3(3).
the Os-CH2 group of the inserted one. The subsequent coordi-
nation of the chloride anion to the metal center of the result-
ing five-coordinate species stabilizes the compound. This
σ-bond metathesis between a M-alkyl and an olefin is consistent
with the fact that it is the product M-C bond strengths that
dominate in the determination of the position of the hydro-
carbon activation equilibria and not the reactant C-H bond
strengths.18 Although a HC(sp2)-H bond is stronger than a
RHC(sp3)-H bond, the Os-CHd bond is stronger than the
Os-CH2- bond.
(JHH=9.0 Hz) at 5.65 and 7.99 ppm corresponding to the
C(3)-H and C(2)-H hydrogen atoms, respectively. In the
13C{1H} NMR spectrum, the C(3) resonance appears at
142.9 ppm, as a doublet with a C-P coupling constant of
15.7 Hz, whereas the C(2) signal is observed at 126.8 ppm as a
singlet. The 31P{1H} NMR spectrum contains a singlet at
15.9 ppm.
Complex 4, which is isolated as a white solid in 67% yield,
has been characterized by X-ray diffraction analysis. A view of
the structure of the molecule is shown in Figure 2. The coordi-
nation geometry around the osmium atom can be rationalized
as a distorted octahedron with the phosphorus atom of the
triisopropylphosphine group and the nitrogen atom of the
resulting n-propylamine ligand occupying mutually trans
positions (P-Os-N(2)=176.43(7)°). The perpendicular plane
is formed by the atoms C(3) and N(1) of the activated allyla-
mine group, which acts with a bite angle C(3)-Os-N(1) of
78.31(11)°, the chloride ligand trans disposed to C(3) (Cl-
Os-C(3)=160.32(9)°) and the carbonyl group trans disposed
to N(1) (C(7)-Os-N(1)=171.49(11)°). The Os-C(3) bond
The M-alkylidene to M-olefin rearrangement is in most
cases an exothermic process, in particular for cationic species
containing an alkylidene ligand with β-CH bonds.21 How-
ever, some systems showing alkylidene preference have
been found.22 Some cationic osmium metal fragments seem
to be a part of these systems, revealing a marked tendency
to stabilize the alkylidene form with regard to the olefin.23
In addition, electron-rich osmium metal fragments effi-
ciently promote the electrophilicity transfer from CR to Cβ
(21) See for example: (a) Cutler, A.; Fish, R. W.; Giering, W. P.;
Rosenblum, M. J. Am. Chem. Soc. 1972, 94, 4354. (b) Casey, C. P.; Albin,
L. D.; Burkhardt, T. J. J. Am. Chem. Soc. 1977, 99, 2533. (c) Brookhart, M.;
Tucker, J. R.; Husk, G. R. J. Am. Chem. Soc. 1981, 103, 979. (d) Casey, C. P.;
Miles, W. H.; Tukada, H. J. Am. Chem. Soc. 1985, 107, 2924. (e) Alias,
F. M.; Poveda, M. L.; Sellin, M.; Carmona, E. J. Am. Chem. Soc. 1998, 120,
5816.
2
˚
length of 2.040(3) A compares well with the Os-C(sp ) single-
bond distances found in other osmium-alkenyl complexes,19
˚
whereas the C(3)-C(2) bond length of 1.343(4) A agrees
well with the average carbon-carbon double-bond distance
(1.32(1) A).20 In accordance with the sp2 hybridization at C(3)
˚
(22) See for example: (a) Coalter, J. N., III; Bollinger, J. C.; Huffman,
ꢀ
J. C.; Werner-Zwanziger, U.; Caulton, K. G.; Davidson, E. R.; Gerard,
and C(2), the Os-C(2)-C(3) and C(3)-C(2)-C(1) angles are
118.3(2)° and 120.3(3)°, respectively.
H.; Clot, E.; Eisenstein, O. New J. Chem. 2000, 24, 9. (b) Coalter, J. N., III;
Ferrando, G.;Caulton, K. G. New J. Chem. 2000, 24, 835. (c) Coalter, J. N., III;
Huffman, J. C.; Caulton, K. G. Organometallics 2000, 19, 3569. (d) Coalter,
J. N., III; Huffman, J. C.; Streib, W. E.; Caulton, K. G. Inorg. Chem. 2000, 39,
3757. (e) Coalter, J. N., III; Streib, W. E.; Caulton, K. G. Inorg. Chem. 2000,
The 1H, 13C{1H}, and 31P{1H} NMR spectra of 4 are con-
sistent with the structure shown in Figure 2. In the 1H NMR
spectrum, the most noticeable resonances are two doublets
ꢀ
39, 3749. (f) Ferrando, G.; Gerard, H.; Spivak, G. J.; Coalter, J. N., III;
Huffman, J. C.; Eisenstein, O.; Caulton, K. G. Inorg. Chem. 2001, 40, 6610.
(g) Padilla-Martínez, I. I.; Poveda, M. L.; Carmona, E.; Monge, M. A.; Ruiz-
Valero, C. Organometallics 2002, 21, 93. (h) Ferrando-Miguel, G.; Coalter,
(18) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91.
(19) 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,
ꢀ
J. N., III; Gerard, H.; Huffman, J. C.; Eisenstein, O.; Caulton, K. G. New J.
ꢀ
Chem. 2002, 26, 687. (i) Ferrando, G.; Coalter, J. N., III; Gerard, H.; Huang,
D.; Eisenstein, O.; Caulton, K. G. New J. Chem. 2003, 27, 1451. (j) Ozerov,
O. V.; Watson, L. A.; Pink, M.; Caulton, K. G. J. Am. Chem. Soc. 2003, 125,
9604. (k) Ozerov, O. V.; Watson, L. A.; Pink, M.; Caulton, K. G. J. Am. Chem.
Soc. 2004, 126, 6363. (l) Paneque, M.; Poveda, M. L.; Santos, L. L.; Carmona,
ꢀ
~
M. L.; Esteruelas, M. A.; Lopez, A. M.; Onate, E. Organometallics 1997, 16,
ꢀ
~
3169. (e) Esteruelas, M. A.; García-Yebra, C.; Olivan, M.; Onate, E.; Tajada,
ꢀ
M. A. Organometallics 2000, 19, 5098. (f) Castarlenas, R.; Esteruelas,
E.; Lledos, A.; Ujaque, G.; Mereiter, K. Angew. Chem., Int. Ed. 2004, 43,
~
M. A.; Onate, E. Organometallics 2001, 20, 2294. (g) Eguillor, B.;
3708. (m) Hirsekorn, K. F.; Veige, A. S.; Marshak, M. P.; Koldobskaya, Y.;
Wolczanski, P. T.; Cundari, T. R.; Lobkovsky, E. B. J. Am. Chem. Soc. 2005,
127, 4809. (n) Kuznetsov, V. F.; Abdur-Rashid, K.; Lough, A. J.; Gusev, D. G.
J. Am. Chem. Soc. 2006, 128, 14388. (o) Besora, M.; Vyboishchikov, S. F.;
ꢀ
~
Esteruelas, M. A.; Olivan, M.; Onate, E. Organometallics 2005, 24, 1428.
~
~
(h) Bolano, T.; Castarlenas, R.; Esteruelas, M. A.; Onate, E. J. Am. Chem.
Soc. 2006, 128, 3965.
(20) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
ꢀ
Lledos, A.; Maseras, F.; Carmona, E.; Poveda, M. L. Organometallics 2010,
D. G.; Taylor, R. J. Chem. Soc., Dalton Trans. 1989, S1.
29, 2040.

6302 Organometallics, Vol. 29, No. 23, 2010
Baya et al.
in coordinated alkenyl ligands.3c In agreement with both the
alkylidene preference of the [OsCl(CO)(nPrNH2)(PiPr3)]þ
metal fragment and the efficient nucleophilicity transfer
from C(3) to C(2) in 4, the addition of 1.2 equiv of
Scheme 2
HBF4 OEt2 to the diethyl ether solutions of the latter causes
3
the instantaneous precipitation of the alkylidene derivative
[OsCl(dCHCH2CH2NH2)(CO)(nPrNH2)(PiPr3)]BF4 (5) as
a brown solid in 67% yield (Scheme 1). Its formation is
strongly supported by the 1H and 13C{1H} NMR spectra of
the obtained solid in dichloromethane-d2. The first of them
shows at 17.88 ppm a multiplet corresponding to the OsdCH
hydrogen, whereas the second one contains at 296.3 ppm a
doublet with a C-P coupling constant of 6.3 Hz due to the
Os-C carbon atom. A singlet at 26.4 ppm in the 31P{1H}
NMR spectrum is also characteristic of 5.
3. Amine-Allene Assembly. The addition of 3.0 equiv of
1-methyl-1-(trimethylsilyl)allene or 1,1-dimethylallene to an
NMR tube containing a dichloromethane-d2 solution of 4
does not produce any change in the H, 13C{1H}, and 31P-
1
ratio between them suggests an angle between the CO ligands
of about 90°.25 The 13C{1H} NMR spectrum contains two
resonances at 183.4 and 182.1 ppm, which appear as doublets
with C-P coupling constants of 5.9 and 9.3 Hz, respectively.
The Os-C and C(sp2) signals of the activated amine are
observed at 154.8 and 138.8 ppm. The first of them is a
doublet with a C-P coupling constant of 8.1 Hz, whereas the
second one appears as a singlet. These C-P coupling con-
stant values support the cis disposition of the phosphine
ligand to the carbonyl groups and the metalated atom of the
amine. In the 31P{1H} NMR spectrum, the phosphine ligand
displays a singlet at 18.2 ppm.
Complex 6 reacts with 1-methyl-1-(trimethylsilyl)allene
and 1,1-dimethylallene, as expected, in contrast to 4. Treat-
ment of dichloromethane solutions of 6 with 3.0 equiv
of 1-methyl-1-(trimethylsilyl)allene and 1,1-dimethylallene
at 60 °C for 24 h leads to the diaminoallyl derivatives
{1H} NMR spectra of this compound. Since it has been
proven that carbon monoxide triggers H-C, C-C, and
C-heteroatom reductive couplings without elimination
from the coordination sphere of the metal,19,24 we decided
to replace the chloride ligand of 4 by a carbonyl group in
order to assemble the coordinated amines with the allenes.
Treatment for 3 h at room temperature of dichloromethane
solutions of 4 with 2.0 equiv of TlPF6 under CO atmosphere
gives rise to the precipitation of TlCl and the formation of
the cis-dicarbonyl derivative [Os(CHdCHCH2NH2)(CO)2-
(nPrNH2)(PiPr3)]PF6 (6), which is isolated as a white solid
in 71% yield, according to eq 2.
[Os{η3-CH2C(CHMeR)CHCH(NHnPr)CH2NH2}(CO)2-
(PiPr3)]PF6 (R =SiMe3 (7), Me (8)), asa result of the assembly
of the allenes with the amines. Complexes 7 and 8 are isolated
as white solids in 62% and 58% yield, respectively, according
to Scheme 2.
The presence of two cis carbonyl ligands in 6 is strongly
supported by its IR and 13C{1H} NMR spectrum. The IR
shows two ν(CO) bands at 2015 and 1936 cm-1. The intensity
Figure 3 shows a view of the cation of 7. The structure
proves the assembly of the organic fragments on the coordi-
nation sphere of the metal. The process gives rise to an allyl
ligand with a diamine pendant group, which coordinates
by one of the nitrogen atoms. Thus, the polyhedron around
the osmium atom can be rationalized as being derived from
a highly distorted octahedron with the C(14)-O(1) carbonyl
group trans disposed to the N(1) nitrogen atom of the pen-
dant diamine (C(14)-Os-N(1) = 175.4(2)°). The allyl group
occupies two cis positions with a C(1)-Os-C(10) angle of
65.7(2)°. The terminal carbon atom C(1) is trans disposed
to the C(15)-O(2) carbonyl group (C(1)-Os-C(15) =
162.3(2)°), whereas the substituted C(10) carbon atom lies trans
to the phosphine (C(10)-Os-P = 163.33(17)°). The pendant
diamine substituent is anti with regard to the C(2)-C(3) bond
with a torsion angle C(3)-C(2)-C(10)-C(9) of 138(7)°. The
C(1)-C(2)-C(10) angle is 117.1(6)°. The allyl moiety coordi-
nates in an asymmetrical fashion, with the separation between
ꢀ
~
(23) (a) Esteruelas, M. A.; Lahoz, F. J.; Lopez, A. M.; Onate, E.; Oro,
L. A. Organometallics 1994, 13, 1669. (b) Esteruelas, M. A.; Oro, L. A.;
Valero, C. Organometallics 1995, 14, 3596. (c) Esteruelas, M. A.; Lahoz,
~
F. J.; Onate, E.; Oro, L. A.; Valero, C.; Zeier, B. J. Am. Chem. Soc. 1995,
117, 7935. (d) Albeniz, M. J.; Esteruelas, M. A.; Lledos, A.; Maseras, F.;
Onate, E.; Oro, L. A.; Sola, E.; Zeier, B. J. Chem. Soc., Dalton Trans. 1997,
181. (e) Crochet, P.; Esteruelas, M. A.; Lopez, A. M.; Martínez, M.-P.; Olivan,
M.; Onate, E.; Ruiz, N. Organometallics 1998, 17, 4500. (f) Spivak, G. J.;
Caulton, K. G. Organometallics 1998, 17, 5260. (g) Buil, M. L.; Esteruelas,
M. A. Organometallics 1999, 18, 1798. (h) Esteruelas, M. A.; Olivan, M.;
Onate, E.; Ruiz, N.; Tajada, M. A. Organometallics 1999, 18, 2953. (i) Buil,
ꢀ
ꢀ
~
ꢀ
ꢀ
~
ꢀ
~
ꢀ
ꢀ
M. L.; Esteruelas, M. A.; García-Yebra, C.; Gutierrez-Puebla, E.; Olivan, M.
Organometallics 2000, 19, 2184. (j) Baya, M.; Esteruelas, M. A. Organo-
metallics 2002, 21, 2332. (k) Castro-Rodrigo, R.; Esteruelas, M. A.; Fuertes,
ꢀ
~
S.; Lopez, A. M.; Mozo, S.; Onate, E. Organometallics 2009, 28, 5941.
ꢀ
(24) (a) Olivan, M.; Eisenstein, O.; Caulton, K. G. Organometallics
ꢀ
1997, 16, 2227. (b) Huang, D.; Olivan, M.; Huffman, J. C.; Eisenstein, O.;
Caulton, K. G. Organometallics 1998, 17, 4700. (c) Spivak, G. J.; Coalter,
J. N.; Olivan, M.; Eisenstein, O.; Caulton, K. G. Organometallics 1998, 17,
999. (d) Castarlenas, R.; Esteruelas, M. A.; Onate, E. Organometallics 2001,
20, 2294. (e) Bolano, T.; Castarlenas, R.; Esteruelas, M. A.; Modrego, F. J.;
ꢀ
~
~
˚
~
~
Onate, E. J. Am. Chem. Soc. 2005, 127, 11184. (f) Bolano, T.; Castarlenas,
the substituted carbon atom C(10) and the metal (2.239(7) A)
being shorter than the separation between the metal and C(1)
~
R.; Esteruelas, M. A.; Onate, E. J. Am. Chem. Soc. 2009, 131, 2064.
(25) [I(higher ν)]/[I(lower ν)] = cot2 ϑ; see: Crabtree, R. H. The
Organometallic Chemistry of the Transition Metals; 4th ed.; Wiley Inter-
science: NJ, 2005; Chapter 10, p 298.
˚
˚
(2.268(6) A) and C(2) (2.275(6) A). The carbon-carbon dis-
˚
tances within the allylic moiety, 1.418(8) A for C(1)-C(2) and

Article
Organometallics, Vol. 29, No. 23, 2010 6303
Scheme 3
Figure 3. Thermal ellipsoid drawing of the cation of 7, with ellip-
soids at 50% probability. Some hydrogen atoms have been omitted
˚
for clarity. Selected bond lengths (A) and angles (deg): Os-N(1)
carbon monoxide atmosphere. The substitution leads to the
2.182(6);Os-C(1) 2.268(6);Os-C(2) 2.275(6);Os-C(10) 2.239(7);
C(1)-C(2) 1.418(8); C(2)-C(10) 1.447(9); C(9)-C(10) 1.520(9);
N(2)-C(9) 1.483(9); P-Os-C(10) 163.33(17); N(1)-Os-C(14)
175.4(2); C(1)-Os-C(15) 162.3(2); C(1)-Os-C(10) 65.7(2);
C(1)-C(2)-C(10) 117.1(6); C(2)-C(10)-C(9) 125.9(6).
cis-dicarbonyl derivative Os(CHdCHCH2NH2)Cl(CO)2-
(PiPr3) (9), which is isolated as a white solid in 72% yield.
In agreement with the presence of two cis-carbonyl ligands
in the complex, its IR shows two ν(CO) bands at 1999 and
1917 cm-1 with an intensity ratio that is consistent with an
angle between the carbonyl ligands of about 90°. In the
13C{1H} NMR spectrum, the inequivalent carbonyl ligands
display two doublets at 178.4 and 181.6 ppm. The C-P
coupling constant values of 8.3 and 5.3 Hz support the cis
disposition of the phosphine ligand to both carbonyl groups.
The Os-C and C(sp2) resonances of the metallacycle are
observed as doublets at 154.5 and 135.0 ppm, respectively.
The C-P coupling constant values of 17.0 and 12.1 Hz are
also consistent with a cis disposition of the phosphine to the
metalated carbon atom. The 31P{1H} NMR spectrum shows
a singlet at 22.7 ppm.
˚
1.447(9) A for C(2)-C(10), are in accordance with the values
found in other osmium π-allyl derivatives.16e,26
The 1H, 13C{1H}, and 31P{1H} NMR spectra of 7 and 8 are
consistent with the structure shown in Figure 3. In the 1HNMR
spectra the most noticeable resonances are those corresponding
to the allylic hydrogen atoms, which appear at 2.68, 3.91, and
5.25 ppm (7) and 2.64, 3.75, and 5.27 ppm (8). In the 13C{1H}
NMR spectra, the resonances due to the allylic skeleton of 7 are
observed at 47.0 (CH2), 71.0 (CH), and 130.0 (C) ppm, whereas
those of 8 appear at 46.3 (CH2), 71.3 (CH), and 124.7 (C) ppm.
In the 31P{1H} NMR spectra, the phosphine ligands display
singlets at 24.5 (7) and 25.8 (8) ppm.
Treatment of dichloromethane solutions of 9with3.0equivof
TlPF6 in the presence of 3.0 equiv of 1-methyl-1-(trimethylsilyl)-
Complexes 7 and 8 result from the coupling of the central
carbon atom of the allenes and the metalated carbon atom
of 6, the addition of one of the NH-hydrogen atoms of the
generated n-propylamine to the substituted carbon atom of the
allenes, and the attack of the resulting nPrNH-amido group to
the internal C(sp2) atom of the metallacycle of 6. The formation
of the new bonds can be rationalized according to Scheme 2.
The addition of the allenes to the dichloromethane solutions of
6 should initially produce the replacement of the n-propylamine
ligand by the less congested C-C double bond of the allenes.27
Thus, the subsequent migratory insertion of the coordinated
double bond into the Os-C(sp2) bond of the heterometalla-
cycle could generate the π-allyl intermediate B, which should
finally undergo an anti-Markovnikov type 1,4-addition of one
of the NH bonds of the released n-propylamine ligand to the
olefin-allyl unit, affording 7 and 8. Although the hydrogen
atom of the amine could be added to both terminal carbon
atoms of the allyl skeleton, it should be noted that the addition
selectively occurs at the substituted one. In order to corroborate
this proposal, intermediate B with R = SiMe3 (complex 10) has
been prepared by means of the reaction sequence shown in
Scheme 3.
allene leads after 1 h to [Os{η3-CH2C(CHdCHCH2NH2)-
C(SiMe3)CH3}(CO)2(PiPr3)]PF6 (10), as a result of the inser-
tion of the allene into the Os-C(sp2) bond of 9. Complex 10 is
isolated as a white solid in 82% yield.
The structure of 10 determined by X-ray diffraction analy-
sis has two chemically equivalent but crystallographically
independent cations in the asymmetric unit. A drawing of
one of them is shown in Figure 4. The insertion of the allene
into the metallacycle of 9 generates an allyl ligand, coordi-
nated by C(1), C(2), and C(3), with a pendant C(10)-bonded
allylamine substituent at the central carbon atom C(2).
The polyhedron around the osmium atom can be rationa-
lized as a distorted octahedron similar to that of 7, with the
C(11)-O(1) carbonyl ligand trans disposed to the pendant N(1)
nitrogen atom (C(11)-Os(1)-N(1) =175.6(6)° and 174.9(6)°).
The allyl unit occupies two cis positions with C(1)-Os(1)-C(3)
angles of 66.6(5)° and 65.5(6)°. The terminal carbon atom C(1)
is trans disposed to the C(12)-O(2) carbonyl group (C(1)-
Os(1)-C(12)=158.1(6)° and 157.3 (6)°), whereas C(3) lies
trans to the phosphine (C(3)-Os(1)-P(1) = 169.8(4)° and
169.3(4)°). The pendant amine is syn disposed with regard to
the methyl substituent at C(3) (C(10)-C(2)-C(3)-C(4) =
10(2)° and 7(2)°) and anti with regard to the trimethylsilyl
group (C(10)-C(2)-C(3)-Si(1) = 129(1)° and 135(1)°). The
C(1)-C(2)-C(3) angles are 120.1(13)° and 119.3(13)°. The
allyl moiety coordinates in an asymmetrical fashion, with
the separation between C(3) and the metal (2.324(14) and
The n-propylamine ligand of 4 can be displaced by a CO
molecule in dichloromethane at room temperature under
~
(26) See for example: (a) Baya, M.; Esteruelas, M. A.; Onate, E.
ꢀ
Organometallics 2001, 20, 4875. (b) Esteruelas, M. A.; Gonzalez, A. I.;
ꢀ
ꢀ
~
Lopez, A. M.; Olivan, M.; Onate, E. Organometallics 2006, 25, 693.
ꢀ
~
(27) Collado, A.; Esteruelas, M. A.; Lopez, F.; Mascarenas, J. L.;
~
Onate, E.; Trillo, B. Organometallics 2010, 29, 4966.

6304 Organometallics, Vol. 29, No. 23, 2010
Baya et al.
[Os{η3-CH2C[CHMe(SiMe3)]CHCH(NHPh)CH2NH2}(CO)2-
(PiPr3)]PF6 (11), which is isolated as a white solid in 75% yield.
The presence of a PhNH group in the diaminoallyl ligand of
11 is strongly supported by the 1H and 13C{1H} NMR spectra
of this compound, which contain the corresponding phenyl
signals. In agreement with 7and 8, the1HNMRspectrumshows
the allylic hydrogen resonances at 2.30, 3.97, and 5.28 ppm,
whereas in the 13C{1H} NMR spectrum the resonances due
to the allylic skeleton are observed at 45.2 (CH2), 68.5 (CH),
and 130.0 (C) ppm. A singlet at 23.4 ppmin the 31P{1H} NMR
spectrum is also characteristic of this compound.
Concluding Remarks
This study has revealed that two molecules of allylamine
and gem-disubstituted allenes can be assembled on the co-
ordination sphere of osmium to afford allyl ligands with a
pendant diamine group, which coordinate to the metal center
by the allyl unit and one of the nitrogen atoms of the diamine
substituent. Starting from the complex OsH2Cl2(PiPr3)2, the
process has been carried out by means of the efficient con-
catenation of four relevant reactions: (i) the hydrometalation
of the carbon-carbon double bond of one of the amines; (ii)
the reduction of the metalated amine by hydrogen-atom
transfer from the other one, which is metalated by means of
C(sp2)-H bond activation; (iii) the insertion of the allene into
the Os-C(sp2) bond of the resulting heterometallacycle to
give an allyl ligand with a pendant C3-bonded allylamine
substituent; and (iv) the regio- and stereoselective 1,4 addition
of a N-H bond of the reduced amine to the olefin-allyl unit of
the allyl C3-bonded allylamine ligand. The replacement of the
reduced amine for the other amine in the last step allows
preparing allyl ligands with different amino substituents at the
C2-carbon atom of the pendant group.
Figure 4. Thermal ellipsoid drawing of one of the two independent
molecules of complex 10, with ellipsoids at 50% probability. Some
hydrogen atoms have been omitted for clarity. Selected bond
˚
lengths (A) and angles (deg): Os(1)-N(1) 2.197 (12), 2.196(12);
Os(1)-C(1) 2.260(17), 2.256(15); Os(1)-C(2) 2.302(12), 2.319(13);
Os(1)-C(3) 2.324(14), 2.340(16); C(1)-C(2) 1.434(18), 1.470(2);
C(2)-C(3) 1.470(19), 1.41(2); C(9)-C(10) 1.33(2), 1.32(3); P(1)-
Os(1)-C(3) 169.8(4), 169.3(4); N(1)-Os(1)-C(11) 175.6(6),
174.9(6); C(1)-Os(1)-C(12) 158.1(6), 157.3(6); C(1)-Os(1)-C(3)
66.6(5), 65.5(6); C(1)-C(2)-C(3) 120.1(13), 119.3(13); C(2)-
C(3)-C(4) 115.3(12), 115.6(13); C(2)-C(3)-Si(1) 123.7(10),
124.9(12).
˚
2.340(16) A) being longer than those between the metal
˚
and C(1) (2.260(17) and 2.256(15) A) and C(2) (2.302(12)
˚
and 2.319(13) A). The carbon-carbon distances within the
˚
allyl moiety, 1.434(18) and 1.471(2) A for C(1)-C(2) and
˚
1.470(19) and 1.41(2) A for C(2)-C(3), agree well with those
˚
of 7. The C(9)-C(10) bond lengths of 1.33(2) and 1.32(3) A
support the presence of a double bond between these atoms
Experimental Section
General Methods and Instrumentation. All reactions were
carried out under argon with rigorous exclusion of air using
Schlenk-tube or glovebox techniques. Solvents were dried by the
usual procedures and distilled under argon prior to use. The
starting material OsH2Cl2(PiPr3)2 (1) was prepared according to
the published method.28 All reagents were obtained from com-
mercial sources. Unless stated, NMR spectra were recorded on a
Varian Gemini 2000, a Bruker ARX 300, or a Bruker Avance
300 MHz instrument, with resonating frequencies of 300 MHz
(1H), 121.5 MHz (31P), and 75.5 MHz (13C). Chemical shifts
(expressed in parts per million) are referenced to residual solvent
peaks (1H, 13C) or external H3PO4 (31P). Coupling constants, J,
are given in hertz. Infrared spectra were run on a Perkin-Elmer
Spectrum 100 FT-IR spectrometer. C, H, and N analyses were
carried out in a Perkin-Elmer 2400 CHNS/O analyzer. High-
resolution electrospray mass spectra were acquired using a
MicroTOF-Q hybrid quadrupole time-of-flight spectrometer
(Bruker Daltonics, Bremen, Germany).
of the pendant substituent.
The 1H, 13C{1H}, and 31P{1H} NMR spectra of 10 are con-
sistent with the structure shown in Figure 4. In the 1H NMR
spectrum the resonances due to the C(1)H2-hydrogen atoms
are observed at 6.00 and 6.70 ppm. In the 13C{1H} NMR
spectrum the allylic resonances appear at 35.5 (C(1)), 64.5
(C(3)), and 127.8 (C(2)) ppm, whereas the olefinic C(9) and
C(10) signals are observed at 126.9 and 130.1 ppm, respec-
tively. The 31P{1H} NMR spectrum shows the phosphine
resonance at 22.3 ppm.
Complex 10 reacts with 1.0 equiv of n-propylamine in
dichloromethane at room temperature to give 7 in quantita-
tive yield, as a result of the addition of one of the NH hydrogen
atoms to the allylic carbon atom C(3) and the nPrNH-amido
group to the olefinic carbon atom C(9). The comparison of
the stereochemistries of the diamineallyl and amineallyl ligands
of 7 and 10, respectively, suggests that the formation of 7implies
a stepwise 1,4-conjugated addition in which the nuclephil-
lic attack of the amine takes place at the exo face of the
C-C double bond. The second step would consist of the
diastereoselective proton transfer to the C(3) carbon of the
C(Me)SiMe3 moiety.
The formation of 7 by addition of n-propylamine to 10 not
only is a strong evidence in favor of the mechanistic proposal
shown in Scheme 2 but also opens the door to the preparation of
species related to 7and 8with a substituent different from nPrNH.
In fact, complex 10 reacts with aniline in dichloromethane to give
Preparation of Os(CH2CH2CH2NH2)Cl(η2-CH2dCHCH2NH2)-
j
jj
(PiPr3) (2). Allylamine (300 μL, 3.90 mmol) was added to a suspen-
sion of 1 (540 mg, 0.93 mmol) in toluene (15 mL). The mixture
immediately turned into a yellow solution. After 20 h of stirring, a
yellowish suspension was obtained, which was vacuum-dried, and
the residue was extracted with dichloromethane (50 mL). The result-
ing solution was vacuum-dried, washed with cold methanol (273 K,
3ꢁ 4mL) andpentane(4ꢁ 4 mL), and dried in vacuo. Ayellowsolid
ꢀ
(28) Aracama, M.; Esteruelas, M. A.; Lahoz, F. J.; Lopez, J. A.;
Meyer, U.; Oro, L. A.; Werner, H. Inorg. Chem. 1991, 30, 288.

Article
Organometallics, Vol. 29, No. 23, 2010 6305
was obtained. Yield: 301 mg (0.60 mmol, 65%). Anal. Calcd for
C15H36ClN2OsP: C, 35.95; H, 7.24; N, 5.59. Found: C, 36.28; H, 6.85;
N, 5.78. IR (cm-1): 3322, 3225, 3129 (m, NH). 1H NMR (CD2Cl2,
plus COSY): δ0.58 (br, 1H, NH); 1.16 (dd, 3JHP = 11.1, 3JHH =7.2,
9H, PCHCH3); 1.20 (dd, 3JHP = 11.1, 3JHH = 7.5, 9H, PCHCH3);
1.26 (partially hidden, 1H, Os-CH2-);1.46(m, 2H, Os-CH2-CH2-);
1.64 (dd, 3JHH=8.1, 2JHH=3.0, 1H, dCH2); 2.10 (m, 3H, PCHCH3);
2.13 (partially hidden, 1H, Os-NH2-CH2-CH2-); 2.43 (br, 1H, NH);
2.90 (ddd, 3JHH=7.5, 3JHH=6.9, 3JHH=6.9, 1H, -CHdCH2); 2.99
25 μL, 0.18 mmol) was added to a solution of 4 (82 mg, 0.15 mmol)
in diethyl ether (8 mL). A pale brown precipitate immediately
appeared, which was decanted, washed with diethyl ether (4 ꢁ
5 mL), and dried in vacuo. A pale brown solid was obtained. Yield:
75 mg (0.10 mmol, 67%). Anal. Calcd for C16H37BClF4N2OOsP:
C, 31.15; H, 6.04; N, 4.54. Found: C, 31.37; H, 5.76; N, 4.60. IR
(cm-1): 3289 (w, NH); 1958 (s, CO) 1030 (vs, BF4-). H NMR
1
(CD2Cl2, plus COSY): δ 0.87 (t, 2JHH = 7.5 Hz, 3H, -CH2CH2-
CH3), 1.03 (dd, 3JHP = 12.9 Hz, 3JHH = 7.5 Hz, 9H, PCHCH3),
1.42 (dd, 3JHP = 12.9 Hz, 3JHH = 7.5 Hz, 9H, PCHCH3), 1.45 (m,
2H, -CH2CH2CH3), 1.48 (m, 1H, OsdCH-CH2-), 2.41 (m, 3H,
PCHCH3), 2.61 (m, 1H, -CH2CH2CH3), 2.81 (m, 1H, OsdCH-
CH2-), 2.89 (m, 1H, -CH2CH2CH3), 3.07 (m, 1H, -CH2CH2-
CHdOs), 3.19, 4.00, 4.02, 5.07 (all br, 1H each, NH), 3.80 (m,
1H, -CH2CH2CHdOs), 17.88 (m, 1H, OsdCH-). 13C NMR
(CD2Cl2, plus APT, HSQC and HMBC): δ 10.8 (þ, s, -CH2-
3
2
(m, 1H, NH2-CH2-CHd); 3.35 (m, JHH = 7.5, JHH = 3.0, 1H,
dCH2); 3.69 (m, 1H, Os-CH2-); 3.93 (br, 1H, NH); 4.14 (m, 1H,
NH2-CH2-CHd); 4.48 (dd, 3JHH=9.3, 3JHH=9.3, 1H, NH2-CH2-
CHd); 4.63 (br, 1H, NH). 13C NMR (CD2Cl2, plus APT, HSQC
3
and HMBC): δ 5.9 (d, JHP =3.5, Os-CH2-); 19.8, 20.0 (both s,
1
PCHCH3); 27.2 (d, JCP =14.9, PCH); 29.3 (s, -CHdCH2); 35.5
(d, 2JCP=2.6, -CHdCH2); 35.5 (s, NH2-CH2-CH2-); 47.9 (s, NH2-
CH2-CH2-); 52.8 (d, 3JCP = 3.2, NH2-CH2-CHd). 31P{1H} NMR
(CD2Cl2): δ -7.3 (s).
CH2CH3), 17.8, 19.4 (þ, both br, PCHCH3), 24.3 (þ, d, 1JCP
=
29.4 Hz, PCHCH3), 26.2 (-, s, -CH2CH2CH3), 44.2 (-, s, -CH2-
CH2CHdOs), 53.2 (-, s, -CH2CH2CH3), 63.8 (-, s, -CH2-
CH2CHdOs), 180.9 (-, d, 2JCP = 9.8 Hz, Os-CO), 296.3 (þ, d,
2JCP = 6.3 Hz, OsdCH-). 31P{1H} NMR (CD2Cl2): δ 26.4 (s).
Preparation of [Os(CH2CH2CH2NH2)(CO)(η2-CH2dCHCH2N-
j
jj
H2)(PiPr3)]Cl (3). A solution of 2 (90 mg, 0.18 mmol) in toluene
(8 mL) was stirred in a carbon monoxide atmosphere for 6 h at
0 °C. A white suspension was obtained, which was concentrated to
ca. 0.5 mL. Addition of pentane (4 mL) caused a precipitate, which
was decanted, washed with pentane (3 ꢁ 4 mL), and dried in vacuo.
A white solid was obtained. Yield: 80 mg (0.15 mmol, 84%). Anal.
Calcd for C16H36ClN2OOsP: C, 36.32; H, 6.86; N, 5.29. Found: C,
36.05; H, 6.42; N, 5.00. IR (cm-1): 3196, 3093 (m, NH); 1945 (vs,
CO). 1H NMR (CD2Cl2, plus COSY): δ 0.77 (br, 1H, NH), 0.88
(m, 1H, Os-CH2-), 1.12 (dd, 3JHP = 12.9 Hz, 3JHH = 7.2 Hz, 9H,
Preparation of [Os(CHdCHCH2NH2)(CO)2(nPrNH2)(PiPr3)]-
PF6 (6). TlPF6 (168 mg, 0.48 mmol) was added to a dichloro-
methane solution (12 mL) of 4 (126 mg, 0.24 mmol) under a
carbon monoxide atmosphere, and the mixture was stirred for 3 h
away from light. The resulting suspension was filtered, and the
solution was vacuum-dried. The residue was washed with pentane
(4 ꢁ 4 mL). A white solid was obtained. Yield: 112 mg (0.17 mmol,
71%). Anal. Calcd for C17H36F6N2O2OsP2: C, 30.63; H, 5.44; N,
4.20. Found: C, 30.89; H, 5.41; N, 4.52. IR (cm-1): 3350, 3317 (w,
NH); 2015, 1936 (s, CO); 831 (vs, PF6-). 1H NMR (CD2Cl2, plus
COSY): δ 0.93 (t, 2JHH=7.8 Hz, 3H, -CH2CH2CH3), 1.24 (dd,
3
3
PCHCH3), 1.16 (dd, JHP = 12.9 Hz, JHH = 7.2 Hz, 9H,
PCHCH3), 1.55 (m, 2H, Os-CH2-CH2-), 2.27 (m, 3H, PCHCH3),
=
2.38 (m, 1H, NH2-CH2-CH2-), 2.54 (dd, 3JHH = 9.9 Hz, 2JHH
3JHP = 14.1 Hz, 3JHH = 7.5 Hz, 9H, PCHCH3), 1.26 (dd, 3JHP
=
14.1 Hz, 3JHH = 7.5 Hz, 9H, PCHCH3), 1.55 (m, 2H, -CH2CH2-
CH3), 2.35 (m, 3H, PCHCH3), 2.89, 3.00 (both m, 1 H each,
-CH2CH2CH3), 3.64, 4.55 (both br, 2 H each, NH), 3.71 (m, 2H,
Os-CHdCH-CH2-), 6.46(d, 2JHH =10.6Hz, 1H, Os-CHdCH-),
7.77 (d, 2JHH = 10.6Hz, 1H, Os-CHdCH-). 13CNMR (CD2Cl2,
plus APT, HSQC, and HMBC): δ 10.4 (þ, s, -CH2CH2CH3),
19.1, 19.2 (þ, both s, PCHCH3), 26.0 (-, s, -CH2CH2CH3), 26.2
1.8 Hz, 1H, -CHdCH2), 2.72 (m, 1H, NH2-CH2-CH2-), 2.89 (d,
1H, -CHdCH2), 2.99 (m, 1H, Os-CH2-), 3.64 (m, 1H, -CHd
CH2), 3.98 (m, 1H, Os-CH2-CHd), 4.14 (br, 1H, NH), 5.11 (dd,
2JHH = 8.7 Hz, 2JHH = 8.7 Hz, 1H, Os-CH2-CHd), 6.33 (br, 1H,
NH), 7.26 (br, 1H, NH). 13C NMR (CD2Cl2, 273 K, plus APT,
HSQC, and HMBC): δ19.5, 19.6 (þ, boths, PCHCH3),26.3(þ, d,
1JCP = 44.2 Hz, PCHCH3), 26.7 (-, d, 2JCP = 10.7 Hz, Os-CH2-),
32.3 (-, s, NH2-CH2-CH2-), 39.9 (-, d, 2JCP = 3.3 Hz, -CHd
1
(þ, d, JCP = 29.5 Hz, PCHCH3), 52.9 (-, s, Os-CHdCH-
CH2), 42.1 (þ, d, 2JCP = 2.7 Hz, -CHdCH2), 49.9 (-, d, 3JCP
=
CH2-), 53.2 (-, s, -CH2CH2CH3), 138.8 (þ, s, Os-CHdCH-),
154.8 (þ, d, 2JCP = 8.1 Hz, Os-CHdCH-), 182.1 (-, d, 2JCP
=
5.3 Hz, NH2-CH2-CHd), 51.3 (-, s, NH2-CH2-CH2-), 187.0 (-,
d, 2JCP = 14.1 Hz, Os-CO). 31P{1H} NMR (CD2Cl2): δ -0.2 (s).
2
9.3 Hz, Os-CO), 183.4 (-, d, JCP = 5.9 Hz, Os-CO). 31P{1H}
NMR (CD2Cl2): δ 18.2 (s, PiPr3), -145.1 (sept, 2JFP = 717.6 Hz,
PF6-).
Preparation of Os(CHdCHCH2NH2)Cl(CO)(nPrNH2)(PiPr3)
(4). A warm (323 K) solution of 3 (120 mg, 0.23 mmol) in toluene
(15 mL) was stirred for 2 h. A white suspension was obtained,
which was concentrated to ca. 0.5 mL. Addition of pentane (4 mL)
caused a precipitate, which was decanted and further washed with
pentane (2 ꢁ 4 mL) and driedin vacuo. A white solid was obtained.
Yield: 80 mg (0.34 mmol, 67%). Anal. Calcd for C16H36ClN2OOsP:
C, 36.32; H, 6.86; N, 5.29. Found: C, 36.39; H, 6.61; N, 5.14. IR
(cm-1): 3354, 3249 (w, NH); 1867 (s, CO). 1H NMR (CD2Cl2, plus
COSY): δ 0.90 (t, 2JHH = 7.5 Hz, 3H, -CH2CH2CH3), 1.22 (dd,
Preparation of [Os{η3-CH2C[CHMe(SiMe3)]CHCH(NHnPr)CH2N-
i
H2}(CO)2(PPr3)]PF6 (7). 3-Trimethylsilyl-1,2-butadiene (85 μL,
0.51 mmol) was added to a solution of 6 (129 mg, 0.19 mmol)
in dichloromethane (6 mL), and the mixture was heated (333 K)
and stirred in a Teflon tube for 24 h. The resulting solution was
vacuum-dried, and the residue was washed with pentane (3 ꢁ
3 mL). A white solid was obtained. Yield: 95 mg (0.12 mmol,
62%). Anal. Calcd for C24H50F6N2O2OsP2Si: C, 36.35; H, 6.36;
N, 3.53. Found: C, 36.25; H, 5.91; N, 3.49. HRMS (ESIþ, m/z):
calcd for C24H50F6N2O2OsP2Si: [M]þ 649.3, found 649.3; calcd
3JHP = 12.9 Hz, 3JHH = 7.5 Hz, 9H, PCHCH3), 1.25 (dd, 3JHP
=
12.9 Hz, 3JHH=7.5 Hz, 9H, PCHCH3), 1.50 (m, 2H, -CH2CH2-
CH3), 2.37 (m, 3H, PCHCH3), 2.43, 3.48, 3.63, 4.46 (all br, 1H each,
NH), 2.76, 2.89 (both m, 1H each, -CH2CH2CH3), 3.62 (m, 2H,
NH2CH2CHd), 5.65 (d, 2JHH = 9.0 Hz, 1H, Os-CHdCH-), 7.99
(d, 2JHH = 9.0 Hz, 1H, Os-CHdCH-). 13C NMR (CD2Cl2, plus
APT, HSQC, and HMBC): δ 11.0 (þ, s, -CH2CH2CH3), 19.3,
19.6 (þ, both s, PCHCH3), 26.2 (þ, d, 1JCP = 27.6 Hz, PCHCH3),
26.5 (-, s, -CH2CH2CH3), 48.5 (-, s, NH2CH2CHd), 49.7 (-,
n
for C18H32F6NO2OsP2: [M þ H - NH2 Pr - SiMe3]þ 518.2,
found 518.2. IR (cm-1): 3339, 3299 (w, NH); 2020, 1954 (vs, CO);
828 (vs, PF6-). H NMR (CD2Cl2, 500.0 MHz, plus COSY): δ
1
2
0.27 (s, 9H, -Si(CH3)3), 0.91 (t, JHH = 7.0 Hz, 3H, -CH2-
CH2CH3), 1.08 (d, 3JHH = 6.5 Hz, 3H, -C6H-C7H3), 1.36 (dd,
=
3JHP = 14.5 Hz, 3JHH = 7.0 Hz, 9H, PCHCH3), 1.41 (dd, 3JHP
3
14.5 Hz, JHH = 7.0 Hz, 9H, PCHCH3), 1.45 (m, 2H, -CH2-
CH2CH3), 2.09 (q, 3JHH = 6.5 Hz, 1H, -C6H-), 2.30-2.50 (both
m, 1H each, -CH2CH2CH3), 2.51 (m, 3H, PCHCH3), 2.56
(m, 1H, -C5H2), 2.68 (br, 1H, NH), 2.88 (m, 1H, -C1H2-),
3.39 (br, 1H, NH), 3.65 (br, 1H, -C2H-), 3.85 (m, 1H, -C1H2-),
3.91 (m, 1H, -C5H2), 5.25 (m, 1H, -C3H-). 13C NMR (CD2Cl2,
s, -CH2CH2CH3), 126.8 (þ,s,Os-CHdCH-), 142.9 (þ,d,2JCP
31P{1H} NMR (CD2Cl2): δ 15.9 (s).
=
2
15.7 Hz, Os-CHdCH-), 188.3 (-, d, JCP = 11.9 Hz, Os-CO).
Preparation of [OsCl(dCHCH2CH2NH2)(CO)(nPrNH2)-
(PiPr3)]BF4 (5). HBF4 (1:1 molar ratio solution in diethyl ether,

6306 Organometallics, Vol. 29, No. 23, 2010
Baya et al.
125.8 MHz, plus APT, HSQC, and HMBC): δ -2.8 (þ,
s, -Si(CH3)3), 11.5 (þ, s, -CH2CH2CH3 and -C7H3), 18.8,
19.0 (þ, both s, PCHCH3), 23.1 (-, s, -CH2CH2CH3), 26.9 (þ,
d, 1JCP = 26.4 Hz, PCHCH3), 34.1 (þ, s, -C6H-), 47.0 (-, d,
2JCP = 2.6 Hz, -C5H2), 50.9 (-, s, -CH2CH2CH3), 57.7 (þ,
18.9 Hz, -C3H-), 130.0 (-, s, -C4-), 177.1 (-, d, 2JCP = 8.0 Hz,
Os-CO), 182.7 (-, s, Os-CO). 31P{1H} NMR (CD2Cl2, 202.5 MHz):
δ 24.5 (s, PiPr3), -145.1 (sept, 2JFP = 717.6 Hz, PF6-).
3JHP=12.6 Hz, 3JHH=7.5 Hz, 9H, PCHCH3), 1.35 (dd, 3JHP
12.6 Hz, JHH = 7.5 Hz, 9H, PCHCH3), 2.65 (m, 3H, PCH-
=
3
CH3), 3.50, 3.95 (both m, 1 H each, Os-CHdCH-CH2-), 4.01,
4.32 (both br, 1 H each, NH), 6.35 (d, 2JHH = 12.0 Hz, 1H, Os-
CHdCH-), 7.66 (d, 2JHH = 12.0 Hz, 1H, Os-CHdCH-). 13
C
s,-C2H-), 59.3(-,d,3JHP =7.2Hz,-C1H2-),71.0(þ,d,2JHP
=
NMR (CD2Cl2, plus APT, HSQC, and HMBC): δ 19.0, 19.4 (þ,
both s, PCHCH3), 25.9 (þ, d, 1JCP = 29.4 Hz, PCHCH3), 54.8
2
(-, s, Os-CHdCH-CH2-), 135.0 (þ, d, JCP = 17.0 Hz, Os-
CHdCH-), 154.5 (þ, d, 2JCP = 12.1 Hz, Os-CHdCH-), 178.0
(-, d, 2JCP = 8.3 Hz, Os-CO), 184.5 (-, d, 2JCP = 5.3 Hz, Os-
CO). 31P{1H} NMR (CD2Cl2): δ 22.7 (s).
Preparation of [Os{η3-CH2C(CHdCHCH2NH2)C(SiMe3)-
CH3}(CO)2(PiPr3)]PF6 (10). TlPF6 (249 mg, 0.71 mmol) was
added to solution of 9 (122 mg, 0.24 mmol) and 3-trimethylsilyl-
1,2-butadiene (120 μL, 0.72 mmol) in dichloromethane (15 mL), and
the mixture was stirred for 1 h. The resulting suspension was filtered,
and the solution was vacuum-dried. The residue was washed with
pentane (4 ꢁ 5 mL). A white solid was obtained. Yield: 147 mg (0.20
mmol, 82%). Anal. Calcd for C21H41F6NO2OsP2Si: C, 34.37; H,
5.63; N, 1.91. Found: C, 33.99; H, 5.65; N, 2.40. IR (cm-1): 3233 (w,
NH); 2015, 1950 (vs, CO); 828 (vs, PF6-). 1H NMR (CD2Cl2, 500.0
Preparation of [Os{η3-CH2C(CHMe2)CHCH(NHnPr)CH2N-
H2}(CO)2(PiPr3)]PF6 (8). 3-Methyl-1,2-butadiene (150 μL,
1.53 mmol) was added to a solution of 6 (250 mg, 0.38 mmol)
in dichloromethane (8 mL), and the mixture was heated (333 K)
and stirred in a Teflon tube for 48 h. The resulting solution was
vacuum-dried, and the residue was washed with pentane (4 ꢁ
5 mL). A white solid was obtained. Yield: 160 mg (0.12 mmol,
58%). Anal. Calcd for C22H44F6N2O2OsP2: C, 35.96; H, 6.04;
N, 3.81. Found: C, 35.61; H, 6.45; N, 4.11. HRMS (ESIþ, m/z):
calcd for C22H44F6N2O2OsP2: [M]þ 591.3, found 591.3. IR
(cm-1): 3341, 3300 (w, NH); 2021, 1951 (vs, CO); 825 (vs, PF6-).
MHz): δ 0.29 (s, 9H, Si(CH3)3), 1.41 (dd, 3JHP = 14.5 Hz, 3JHH
=
7.0 Hz, 18H, PCHCH3), 1.82 (d, 3JHH = 3.0 Hz, 3H, -C7H3), 2.50
(m, 3H, PCHCH3), 2.58 (d, 2JHH = 3.0 Hz, 1H, -C5H2), 3.01 (m,
1H, -C1H2-), 3.03, 3.16 (both br, 1 H each, NH), 3.45 (d, 2JHH
=
3.0 Hz, 1H, -C5H2), 3.80 (m, 1H, -C1H2-), 6.00 (dd, 3JHH = 12.0
Hz, 3JHH = 9.0 Hz, 1H, -C2Hd), 6.70 (d, 3JHH = 12.0 Hz, 1H, d
C3H-).13CNMR(CD2Cl2,plusAPT):δ0.58 (þ,s,Si(CH3)3),18.6
(þ, both s, PCHCH3), 21.1 (þ, s, -C7H3), 25.7 (þ, d, 1JCP = 27.2
2
Hz, PCHCH3), 35.5 (-, d, JCP = 2.3 Hz, -C5H2), 41.5 (-,
1H NMR (CD2Cl2, 400.0 MHz, plus COSY): δ 0.92 (t, 2JHH
=
s, -C1H2),64.5(-,d, 2JCP =7.6Hz, -C6-), 126.9 (þ, s, -C2Hd),
127.8 (-, s, -C4-), 130.1 (þ, s, dC3H-), 178.4 (-, d, 2JCP = 9.8
Hz, Os-CO), 181.6 (-, s, Os-CO). 31P{1H} NMR (CD2Cl2, 202.5
MHz): δ 22.3 (s, PiPr3), -145.1 (sept, 2JFP = 717.6 Hz, PF6-).
7.6 Hz, 3H, -CH2CH2CH3), 1.17, 1.39 (both d, 3JHH = 6.8 Hz,
3H each, -C6H(CH3)2), 1.35 (dd, 3JHP = 14.5 Hz, 3JHH = 6.8
Hz, 9H, PCHCH3), 1.40 (dd, 3JHP = 14.5 Hz, 3JHH = 6.8 Hz,
9H, PCHCH3), 1.45 (m, 2H, -CH2CH2CH3), 2.33 (m, 1H,
-C6H(CH3)2), 2.40-2.60 (both m, 1H each, -CH2CH2CH3),
2.49 (m, 3H, PCHCH3), 2.64 (m, 1H, -C5H2), 2.70, 3.38 (both
br, 3H, NH), 3.03, 3.65 (both m, 1H each, -C1H2-), 3.69 (m,
1H, -C2H-), 3.75 (m, 1H, -C5H2), 5.27 (m, 1H, -C3H-). 13
C
NMR (CD2Cl2, 100.6 MHz, plus APT, HSQC, and HMBC): δ
11.4 (þ, s, -CH2CH2CH3), 18.5, 19.0 (þ, both s, PCHCH3),
21.0, 25.4 (þ, both s, -C6H(CH3)2), 23.0 (-, s, -CH2CH2CH3),
26.4 (þ, d, 1JCP = 27.1 Hz, PCHCH3), 38.3 (þ, s, -C6H(CH3)2),
46.3 (-, d, 2JCP = 2.6 Hz, -C5H2), 49.3 (-, s, -CH2CH2CH3),
57.5 (þ, s, -C2H-), 59.0 (-, s, -C1H2-), 71.3 (þ, d, 2JHP = 16.8
Hz, -C3H-), 124.7 (-, s, -C4-), 177.3 (-, d, 2JCP = 8.8 Hz, Os-
CO), 182.5 (-, s, Os-CO). 31P{1H} NMR (CD2Cl2, 162.0 MHz):
δ 25.8 (s, PiPr3), -143.9 (sept, 2JFP = 717.6 Hz, PF6-).
Preparation of [Os{η3-CH2C[CHMe(SiMe3)]CHCH(NHPh)CH2N-
H2}(CO)2(PiPr3)]PF6 (11). Aniline (28 μL, 0.30 mmol) was added
to a solution of 10 (101 mg, 0.14 mmol) in dichloromethane (10 mL),
and the mixture was heated at 323 K and stirred in a Teflon tube for
24 h. The resulting solution was vacuum-dried, and the residue was
washed with pentane (4 ꢁ 4 mL). A white solid was obtained. Yield:
85 mg (0.11 mmol, 75%). Anal. Calcd for C27H48F6N2O2OsP2Si: C,
39.22; H, 5.85; N, 3.87. Found: C, 38.74; H, 5.83; N, 3.82. HRMS
(ESIþ, m/z): calcd for C27H48F6N2O2OsP2Si [M]þ 683.3, found
683.3. IR (cm-1): 3335, 3298 (w, NH); 2023, 1952 (vs, CO); 829 (vs,
PF6-). 1H NMR (CD2Cl2, 300.0 MHz, plus COSY): δ 0.24 (s, 9H,
Si(CH3)3), 1.08 (d, 3JHH = 6.9 Hz, 3H, -C7H3), 1.38 (dd, 3JHP
=
15.0 Hz, 3JHH = 8.1 Hz, 9H, PCHCH3), 1.40 (dd, 3JHP = 15.0 Hz,
3JHH = 8.1 Hz, 9H, PCHCH3), 2.09 (m, 1H, -C6H-), 2.30 (d,
2JHH = 4.5 Hz, 1H, -C5H2), 2.51 (m, 3H, PCHCH3), 2.68 (1H,
NH), 3.13 (m, 2H, -C1H2), 3.38 (1H, NH), 3.64 (1H, NH), 4.00 (d,
2JHH = 4.5 Hz, 1H, -C5H2), 4.41 (m, 1H, -C2H-), 5.28 (m, 1H,
-C3H-), 6.50 - 7.20 (5H, Ph). 13CNMR(CD2Cl2, 75.5 MHz, plus
APT, HSQC, and HMBC): δ -2.6 (þ, s, Si(CH3)3), 12.1 (þ, s,
-C7H3), 18.6, 19.0 (þ, both s, PCHCH3), 26.6 (þ, d, 1JCP = 26.6
Hz, PCHCH3), 34.3 (þ, s, -C6H-), 45.3 (-, s, -C5H2), 49.5 (-, d,
Preparation of Os(CHdCHCH2NH2)Cl(CO)2(PiPr3) (9). A
solution of 4 (141 mg, 0.27 mmol) in dichloromethane (15 mL)
was stirred in a CO atmosphere for 3 h. A white solution was
obtained, which was concentrated to ca. 0.1 mL. Addition of
pentane (4 mL) caused a precipitate, which was decanted,
washed with pentane (3 ꢁ 4 mL), and dried in vacuo. A white
solid was obtained. Yield: 96 mg (0.19 mmol, 72%). Anal. Calcd
for C14H27ClNO2OsP: C, 33.76; H, 5.46; N, 2.81. Found: C,
34.21; H, 5.09; N, 3.26. IR (cm-1): 3276, 3224 (w, NH); 1999,
1917 (vs, CO). 1H NMR (CD2Cl2, plus COSY): δ 1.32 (dd,
2JHP = 4.2 Hz, -C1H2-), 56.1 (þ, s, -C2H-), 68.5 (þ, d, 2JHP
=
18.6 Hz, -C3H-), 113.0, 118.5, 129.4 (þ, all s, CH’s in Ph), 130.0
(-, s, -C4-), 146.3 (-, s, Cipso Ph), 176.6 (-, d, 2JCP = 8.2 Hz,

Article
Organometallics, Vol. 29, No. 23, 2010 6307
Os-CO), 181.4 (-,s,Os-CO).31P{1H} NMR (CD2Cl2, 121.5 MHz):
δ 23.4 (s, PiPr3), -144.5 (sept, 2JFP = 717.6 Hz, PF6-).
factors were R1 = 0.0425 (8152 observed reflections, I > 2σ(I))
and wR2 = 0.0888; data/restraints/parameters 9156/1/463;
GoF = 1.224. Largest peak and hole: 2.285 and -1.905 e/A .
3
˚
Crystal data for 4: C16H36ClN2OOsP, Mw 529.09, irregular
block, colorless (0.10 ꢁ 0.08 ꢁ 0.08), triclinic, space group P1,
˚
˚
˚
a = 8.3543(7) A, b = 10.6850(9) A, c = 12.0981(10) A, R =
81.4340(10)°, β = 7.2450(10)°, γ = 82.2200(10)°, V =
1000.85(14) A , Z = 2, Dcalc = 1.756 g cm-3, F(000): 524,
3
˚
T = 100(2) K, μ = 6.588 mm-1; 12 604 measured reflections
(2θ: 3-58°, ω scans 0.3°), 4791 unique (Rint = 0.0255); min./
max. transmn factors 0.50/0.62. Final agreement factors were
R1 = 0.0204 (4546 observed reflections, I > 2σ(I)) and wR2 =
0.0455; data/restraints/parameters 4791/0/224; GoF = 0.936.
Structural Analysis of Complexes 2, 4, 7, and 10. X-ray data
were collected on a Bruker Smart APEX CCD diffractometer
equipped with a normal focus, 2.4 kW sealed tube source
3
˚
Largest peak and hole: 0.996 and -0.724 e/A .
Crystal data for 7: C24H50N2O2OsPSi PF6 0.5C4H10O, Mw
829.95, plate, colorless (0.10 ꢁ 0.08 ꢁ 0.01), monoclinic, space
3
3
˚
(Mo radiation, λ = 0.71073 A) operating at 50 kV and 40(7, 10)/
30(2, 4) mA. Data were collected over the complete sphere. Each
frame exposure time was 10 s covering 0.3° in ω. Data were cor-
rected for absorption by using a multiscan method applied with
the SADABS program.29 The structures were solved by direct
methods. Refinement of complexes was performed by full-
matrix least-squares on F2 with SHELXL97,30 including isotro-
pic and subsequently anisotropic displacement parameters.
Crystals of 2 and 4 suitable for X-ray analysis were obtained
by slow vapor diffusion of pentane into toluene solutions of each
compound. Crystals of 7 and 10 suitable for X-ray analysis were
obtained by slow vapor diffusion of diethyl ether into dichlo-
romethane solutions of each compound.
˚
˚
˚
group P21/c, a = 14.676(5) A, b = 15.476(5) A, c = 16.336(5) A,
,
3
β = 109.164(5)°, V = 3505(2) A , Z = 4, Dcalc = 1.573 g cm-3
˚
F(000) = 1676, T = 100(2) K, μ = 3.822 mm-1; 31 965 mea-
sured reflections (2θ: 3-58°, ω scans 0.3°), 8512 unique (Rint
=
0.0815); min./max. transmn factors 0.67/0.96. Final agreement
factors were R1 = 0.0554 (6146 observed reflections, I > 2σ(I))
and wR2 = 0.1022; data/restraints/parameters 8512/17/393;
3
˚
GoF = 1.077. Largest peak and hole: 2.009 and -2.104 e/A .
Crystal data for 10: C21H41NO2OsPSi PF6, Mw 733.78,
irregular block, colorless (0.16 ꢁ 0.14 ꢁ 0.14), monoclinic, space
3
˚
˚
˚
group P21/c, a = 30.456(5) A, b = 12.727(2) A, c = 14.731(3) A,
,
β = 90.440(2)°, V = 5709.7(18) A , Z = 8, Dcalc = 1.707 g cm-3
3
˚
˚
The unit cell parameters of 10 are a = 30.456(5) A, b =
F(000) = 2912, T = 100(2) K, μ 4.678 mm-1; 53 080 measured
˚
˚
12.727(2) A, c = 14.731(3) A, and β (90.440(2)°) is fortuitously
close to 90°. Refinement of the structure converged at unaccep-
table high R factors. A close inspection of the intensities revealed
a pseudomerohedric twining. When the potential twin operator
was included in SHELX, the structure could be satisfactorily
refined with a twining fraction of 0.21. Unfortunately, even with
the correction included, some spurious residual peaks of elec-
tronic density can be shown in the least cycles of refinement.
Crystal data for 2: C15H36ClN2OsP, Mw 501.08, needle, light
yellow (0.50 ꢁ 0.04 ꢁ 0.04), monoclinic, space group P21/c, a =
reflections (2θ: 3-58°, ω scans 0.3°), 13 933 unique (Rint
=
0.0619); min./max. transmn factors 0.40/0.56. Final agreement
factors were R1 = 0.0809 (11 894 observed reflections, I > 2σ(I))
and wR2 = 0.2213; data/restraints/parameters 13 933/18/634;
3
˚
GoF = 1.052. Largest peak and hole: 8.101 and -3.413 e/A .
Acknowledgment. Financial support from the MICINN
of Spain (Projects CTQ2008-00810 and Consolider Ingenio
ꢀ
ꢀ
2010 CSD2007-00006), Diputacion General de Aragon
(E35), and the European Social Fund is acknowledged. M.B.
thanks the Spanish MICINN/Universidad de Zaragoza for
˚
˚
˚
17.0286(19) A, b = 15.1283(17) A, c = 14.5231(16) A, β =
99.836(8)°, V = 3686.4(7) = A , Z = 8, Dcalc = 1.806 g cm-3
,
3
˚
F(000) = 1984, T = 100(2) K, μ = 7.145 mm-1; 45 297 mea-
ꢀ
funding through the “Ramon y Cajal” program.
sured reflections (2θ: 3-58°, ω scans 0.3°), 9156 unique (Rint =
0.0557); min./max. transmn factors 0.43/0.76. Final agreement
Supporting Information Available: X-ray analysis and crystal
structure determinations including bond lengths and angles of
compounds 2, 4, 7, and 10. Pictorial 1H and 31P{1H} spectra of
the new compounds are also included. This material is available
free of charge via the Internet at http://pubs.acs.org.
(29) Blessing, R. H. Acta Crystallogr. 1995, A51, 33. SADABS: Area-
detector absorption correction; Bruker-AXS: Madison, WI, 1996.
(30) SHELXTL Package v. 6.10; Bruker-AXS: Madison, WI, 2000.
Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112.