Reactivity of the imine-vinylidene complexes OsCl2(=C=CHPh)(NH=CR2) (PiPr3)2 [CR2 = CMe2, C(CH2)4CH2]

Article abstract of DOI:10.1021/om001044j

The reactivity of the imine-vinylidene compounds OsCl₂(=C=CHPh)(NH=CR₂) (PⁱPr₃)₂ [CR₂ = CMe₂ (1), C(CH₂)₄CH₂ (2)] toward amines, ⁿBuLi, and HBF₄ has been studied. Complexes 1 and 2 react with triethylamine and diallylamine to give equilibrium mixtures of the corresponding starting materials and the five-coordinate azavinylidene derivatives OsCl(=N=CR₂)(=C=CHPh)(PⁱPr₃)₂ [CR₂ = CMe₂ (3), C(CH₂)₄CH₂ (4)], which are obtained as pure microcrystalline solids by reaction of 1 and 2 with ⁿBuLi. The structure of 3 in the solid state has been determined by an X-ray diffraction study. The geometry around the metal center could be described as a distorted trigonal bipyramid with apical phophines and inequivalent angles within the Y-shaped equatorial plane. The azavinylidene group coordinates in a bent fashion with an Os-N-C angle of 157.2(6)°. Complexes 1 and 2 also react with allylamine and aniline. The reactions initially give 3 and 4. However, the amount of these compounds decreases by increasing the reaction time. This decrease is accompanied with the formation of mixed amine-phosphine compounds OsCl₂(=C=CHPh)(NH=CR₂)(NH₂R′) (PⁱPr₃) [R′ = allyl; CR₂ = CMe₂ (5), C(CH₂)₄CH₂, (6). R′ = Ph; CR₂ = CMe₂ (7), C(CH₂)₄CH₂ (8)]. The structure of 5 in the solid state has been also determined by an X-ray diffraction study. In this case, the geometry around the osmium atom can be rationalized as a distorted octahedron with the amine and phosphine ligands mutually trans disposed and the chlorine ligands mutually cis disposed. The X-ray analysis also shows that the NH-hydrogen atoms of the amine and the chlorines are involved in intra- and intermolecular H?Cl hydrogen bonding. The reactions of 1 and 2 with HBF₄·OEt₂ afford the carbyne derivatives [OsCl₂(≡CCH₂Ph)(NH=CR₂) (PⁱPr₃)₂][BF₄] [CR₂ = CMe₂ (9), C(CH₂)₄CH₂ (10)]. Both 1 and 2 lose the imine ligand to give OsCl₂(=C=CHPh)(PⁱPr₃)₂ (11) in toluene under reflux.

Full text of DOI:10.1021/om001044j

Organometallics 2001, 20, 1545-1554
1545
Rea ctivity of th e Im in e-Vin ylid en e Com p lexes
OsCl2(dCdCHP h )(NHdCR2)(P iP r 3)2 [CR2 ) CMe2,
C(CH2)4CH2]†
Ricardo Castarlenas,‡ Miguel A. Esteruelas,*,‡ Enrique Gutie´rrez-Puebla,§ and
Enrique On˜ate‡
Departamento de Quı´mica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain, and Instituto de Ciencia de
Materiales de Madrid, CSIC, Campus de Cantoblanco, 28049 Madrid, Spain
Received December 6, 2000
The reactivity of the imine-vinylidene compounds OsCl2(dCdCHPh)(NHdCR2)(PiPr3)2
[CR2 ) CMe2 (1), C(CH2)4CH2 (2)] toward amines, nBuLi, and HBF4 has been studied.
Complexes 1 and 2 react with triethylamine and diallylamine to give equilibrium mixtures
of the corresponding starting materials and the five-coordinate azavinylidene derivatives
OsCl(dNdCR2)(dCdCHPh)(PiPr3)2 [CR2 ) CMe2 (3), C(CH2)4CH2 (4)], which are obtained
n
as pure microcrystalline solids by reaction of 1 and 2 with BuLi. The structure of 3 in the
solid state has been determined by an X-ray diffraction study. The geometry around the
metal center could be described as a distorted trigonal bipyramid with apical phophines
and inequivalent angles within the Y-shaped equatorial plane. The azavinylidene group
coordinates in a bent fashion with an Os-N-C angle of 157.2(6)°. Complexes 1 and 2 also
react with allylamine and aniline. The reactions initially give 3 and 4. However, the amount
of these compounds decreases by increasing the reaction time. This decrease is accompanied
with the formation of mixed amine-phosphine compounds OsCl2(dCdCHPh)(NHd
CR2)(NH2R′)(PiPr3) [R′ ) allyl; CR2 ) CMe2 (5), C(CH2)4CH2, (6). R′ ) Ph; CR2 ) CMe2 (7),
C(CH2)4CH2 (8)]. The structure of 5 in the solid state has been also determined by an X-ray
diffraction study. In this case, the geometry around the osmium atom can be rationalized
as a distorted octahedron with the amine and phosphine ligands mutually trans disposed
and the chlorine ligands mutually cis disposed. The X-ray analysis also shows that the NH-
hydrogen atoms of the amine and the chlorines are involved in intra- and intermolecular
H‚‚‚Cl hydrogen bonding. The reactions of 1 and 2 with HBF4‚OEt2 afford the carbyne
derivatives [OsCl2(tCCH2Ph)(NHdCR2)(PiPr3)2][BF4] [CR2 ) CMe2 (9), C(CH2)4CH2 (10)].
Both 1 and 2 lose the imine ligand to give OsCl2(dCdCHPh)(PiPr3)2 (11) in toluene under
reflux.
In tr od u ction
with vinylidenes afford aminocarbene derivatives,9 which
are better described as azoniaalkenyl species.10
Theoretical studies on vinylidene transition metal
complexes have identified the electron deficiency at the
CR atom and the localization of the electron density on
the Câ atom.1 The chemical reactivity of the vinylidene
unit is thus oriented toward electrophiles at Câ and
nucleophiles on CR.2
Transition metal imine compounds are another class
of interesting organometallic complexes,11 which have
been found to be intermediate states during the trans-
formations between amine and nitrile derivatives.12 The
reactivity of N-protio imines has not been extensively
Examples of additions of water,3 alcohols,3g,4 thiols,4b,5
phosphines,6 fluoride,7 and cyanide ions8 have been
reported. Primary amines follow the general trend of
the above-mentioned nucleophiles, and their reactions
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Marvelli, L.; Peruzzini, M.; Romerosa, A.; Rossi, R. Organometallics
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Romerosa, A.; Zanobini, F. J . Am. Chem. Soc. 1996, 118, 4585. (i) Buil,
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† Dedicated to Prof. J uan Bertra´n on the occasion of his 70th
birthday.
‡ Universidad de Zaragoza-CSIC.
§ Instituto de Ciencia de Materiales de Madrid, CSIC.
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10.1021/om001044j CCC: $20.00 © 2001 American Chemical Society
Publication on Web 03/09/2001

1546 Organometallics, Vol. 20, No. 8, 2001
Castarlenas et al.
Sch em e 1
studied. A few experiments show that they can be
deprotonated by action of strong bases such as Kt-
BuO11l,13 or KH.12g
We have previously reported that the dihydride-
dichloro complex OsH2Cl2(PiPr3)2 reacts with acetone
oxime and cyclohexanone oxime, in the presence of
Et3N, to give the dihydride derivatives OsH2Cl(κ2-
ONdCR2)(PiPr3)2 [CR2 ) CMe2, C(CH2)4CH2],14 which
afford the corresponding hydride-azavinylidene-os-
mium(IV) complexes OsHCl2(dNdCR2)(PiPr3)2 by ad-
dition of HCl15 (Scheme 1). Although there were not
precedents for compounds containing both vinylidene
and imine functional groups, we have recently proven
that they can be formed by a novel reaction, the
hydrogen transfer from alkenyl ligands to azavinylidene
groups. Thus, it was shown that the treatment at room
temperature of the hydride-azavinylidene complexes
OsHCl2(dNdCR2)(PiPr3)2 with Ag[CF3SO3] and the
subsequent addition at -25 °C of phenylacetylene leads
to the alkenyl-azavinylidene derivatives [Os{(E)-CHd
CHPh}Cl(dNdCR2)(PiPr3)2][CF3SO3], which by addition
of NaCl afford the imine-vinylidene compounds OsCl2-
(dCdCHPh)(NHdCR2)(PiPr3)2 via the intermediates
Os{(E)-CHdCHPh}Cl2(dNdCR2)(PiPr3)2.16
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The novelty of the imine-vinylidene species prompted
us to investigate their reactivity. In this paper, we
describe the behavior of the complexes OsCl2(dCd
CHPh)(NHdCR2)(PiPr3)2 [CR2 ) CMe2, C(CH2)4CH2] in
n
the presence of amines, BuLi, and HBF4. In addition,
we report the formation of the desired vinylidene
complex OsCl2(dCdCHPh)(PiPr3)2.17
Resu lts a n d Discu ssion
1. R ea ct ion s of OsCl2(dCdCH P h )(NH dCR 2)-
(P iP r 3)2 [CR2 ) CMe2 (1), C(CH2)4CH2 (2)] w ith
Am in es a n d n Bu Li. The behavior of 1 and 2 in the
presence of amines depends on the nature of the amine.
(i) Tr ieth yla m in e. The addition at room tempera-
ture of 1.0 equiv of this amine to dichloromethane-d2
solutions of 1 gives rise to a 1:5 equilibrium mixture of
1 and the five-coordinate azavinylidene compound OsCl-
{dNdC(CH3)2}(dCdCHPh)(PiPr3)2 (3) according to the
1H and 31P{1H} NMR spectra of the mixture. Under the
same conditions, the addition of triethylamine to dichlo-
romethane-d2 solutions of 2 affords a 1:9 equilibrium
mixture of 2 and OsCl{dNdC(CH2)4CH2}(dCdCHPh)(Pi-
Pr3)2 (4). Complexes 3 and 4 are obtained as pure
microcrystalline solids in high yield (about 80%), by
treatment of tetrahydrofuran solutions of 1 and 2,
n
respectively, with 1.1 equiv of BuLi in hexane (eq 1).
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Reactivity of Imine-Vinylidene Complexes
Organometallics, Vol. 20, No. 8, 2001 1547
RuHCl(dCdCH2)(PH3)2;19 however, it contrasts with
that found for the carbene complexes RuCl2(dCR2)-
(PR3)2, in which the carbene ligand occupies the apical
position of a square pyramid.20
The vinylidene ligand is bound to the metal in a
nearly linear fashion, with an Os-C(1)-C(2) angle of
174.7(6)°. The Os-C(1) [1.812(6) Å] and C(1)-C(2)
[1.331(9) Å] bond lengths compare well with those found
in other osmium-vinylidene complexes21 and support
the vinylidene formulation.
The azavinylidene ligand coordinates to the osmium
atom in a bent fashion with an Os-N-C(9) angle of
157.2(6)°. A similar coordination mode has been ob-
served for the azavinylidene ligands of the osmium
complexes [Os{dNdC(Me)tBu}(η6-C6H6)(PiPr3)]PF6 [167-
(2)°, 168(2)°, and 155(2)°]22 and cis-[OsCl2{dNdC(Ph)-
(2-PhCOC6H4)}(terpy)]PF6 [168.2(3)°].23 This type of
structure has been described as corresponding to orga-
nometallic heteroallene type Schiff base derivatives.24
The Os-N distance of 1.873(5) Å is intermediate
between that found in 1 [2.072(7) Å]16 and in the
F igu r e 1. Molecular diagram for OsCl2(dNdCMe2)-
(dCdCHPh)(PiPr3)2 (3). Thermal ellipsoids are shown at
50% probability.
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex
complexes [Os{dNdC(Me)tBu}(η6-C6H6)(PiPr3)]PF6 [1.81-
22
(2) and 1.83(2) Å]
and cis-[OsCl2{dNdC(Ph)(2-
OsCl(dCdCHP h )(dNdCMe2)(P iP r 3)2 (3)
PhCOC6H4)}(terpy)]PF6 [1.812(6) Å],23 while the N-C(9)
distance of 1.237(9) Å is similar to that found in the
above-mentioned compounds.
Os-Cl
2.409(2)
1.812(6)
2.416(2)
1.873(5)
N-C(9)
1.237(9)
1.331(9)
1.531(10)
1.537(10)
Os-C(1)
Os-P(1)
Os-N
C(1)-C(2)
C(9)-C(10)
C(9)-C(11)
In agreement with the presence of the azavinylidene
and vinylidene ligands in 3 and 4, the IR spectra of
these compounds in KBr contain ν(CdN) and ν(OsdCd
C) bands at 1671 (3) and 1655 (4) cm-1, and 1608 (3)
and 1605 (4) cm-1, respectively. In the 1H NMR spectra
of both compounds the most noticeable resonances are
triplets at 3.4 ppm, with H-P coupling constants of
about 2.5 Hz, corresponding to the dCH hydrogen atom
of the phenylvinylidene ligand. In the 13C{1H} NMR
spectra the resonances corresponding to the CR atom of
this ligand appear at about 275.0 ppm as triplets with
C-P coupling constants of about 11 Hz, whereas the
resonances due to the Câ atom are observed at about
113 ppm, also as triplets but with C-P coupling
constants of about 3 Hz. The resonances corresponding
to the CdN carbon atom of the azavinylidene ligands
appear at 153.8 (3) and 158.2 (4), as triplets with C-P
coupling constants of about 2.5 Hz. The 31P{1H} NMR
spectra of both compounds show a singlet at 4.2 ppm.
N-Os-C(1)
N-Os-Cl
115.7(3)
128.2(2)
92.77(3)
116.1(2)
87.7(3)
89.46(3)
174.26(6)
174.7(6)
Os-N-C(9)
157.2(6)
124.6(7)
115.0(7)
124.8(7)
120.2(7)
117(4)
C(1)-C(2)-C(3)
C(10)-C(9)-C(11)
C(10)-C(9)-N
C(11)-C(9)-N
C(1)-C(2)-H(2)
C(3)-C(2)-H(2)
N-Os-P(1)
Cl-Os-C(1)
Cl-Os-P(2)
C(1)-Os-P(2)
P(1)-Os-P(2)
Os-C(1)-C(2)
118(4)
The reaction shown in eq 1 agrees well with the
reactivity of the N-protio imine ligands in transition
metal compounds, which are deprotonated by strong
bases. In this context it should be pointed out that,
although the deprotonation of vinylidene metal species
is a general method to prepare alkynyl derivatives,18
the formation of alkynyl-N-protio imine complexes is not
observed during the formation of 3 and 4. This fact
elegantly proves that under the same conditions the
NH-hydrogen atom of an imine ligand is stronger
Bro¨nsted acid than the dCH hydrogen atom of a
vinylidene group.
Complexes 3 and 4, which are isolated as orange
solids, were characterized by MS, elemental analysis,
IR, and 1H, 13C{1H}, and 31P{1H} NMR spectroscopy.
Complex 3 was further characterized by an X-ray
crystallographic study. A view of the molecular geom-
etry of this complex is shown in Figure 1. Selected bond
distances and angles are listed in Table 1.
(ii) Dia llyla m in e. The pKa of this amine (9.29) is
similar to that of the triethylamine (10.8). As a conse-
quence, the behavior of 1 and 2 in the presence of both
amines is similar. The addition at room temperature of
1.0 equiv of diallylamine to dichlorometane-d2 solutions
of 1 affords a 2:1 equilibrium mixture of 1 and 3,
whereas, under the same conditions, the treatment of
(19) Oliva´n, M.; Eisenstein, O.; Caulton, K. G. Organometallics 1997,
16, 2227. (b) Oliva´n, M.; Clot, E.; Eisenstein, O.; Caulton, K. G.
Organometallics 1998, 17, 3091.
(20) Schwab, P.; Grubbs, R. H.; Ziller, J . W. J . Am. Chem. Soc. 1996,
118, 100.
(21) Huang, D.; Oliva´n, M.; Huffman, J . C.; Eisenstein, O.; Caulton,
K. G. Organometallics 1998, 17, 4700. (b) Bohanna, C.; Buil, M. L.;
Esteruelas, M. A.; On˜ate, E.; Valero, C. Organometallics, 1999, 18,
5176, and references therein.
(22) Werner, H.; Daniel, T.; Mu¨ller, M.; Mahr, N. J . Organomet.
Chem. 1996, 512, 197.
The geometry around the osmium atom can be
rationalized as a distorted trigonal bipyramid with
apical phosphines [P(1)-Os-P(2) ) 174.26(6)°] and
inequivalent angles within the Y-shaped equatorial
plane. The angles C(1)-Os-N, N-Os-Cl, and C(1)-
Os-Cl are 115.7(3)°, 128.2(2)°, and 116.1(2)°, respec-
tively. This Y structure is similar to that calculated for
(23) Brown, S. N. Inorg. Chem. 2000, 39, 378.
(18) Bruce, M. I.; Swincer, A. G.Adv. Organomet. Chem. 1983, 22,
59. (b) Bitcon, C.; Whiteley, M. W. J . Organomet. Chem. 1987, 336,
385.
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1548 Organometallics, Vol. 20, No. 8, 2001
Castarlenas et al.
Sch em e 2
CH2]Cl to a saturated NaCl acetone-d6 solution of 3
gives rise after 10 min to a 1:4 mixture of 5 and 1 plus
free phosphine. These results suggest that the substitu-
tion process takes place via the previous dissociation of
a chlorine ligand from 1, according to Scheme 3. Since
the formation of 3 is faster than the formation of 5, the
dissociation of phosphine from the intermediate [OsCl-
(dCdCHPh)(NHdCR2)(NH2R′)(PiPr3)2]+ appears to be
the rate-determining step of the substitution.
In contrast to what is expected, during the reactions
shown in Scheme 2, the addition of the primary amine
to the phenylvinylidene ligands of 1-6 is not observed.
This suggests that in these compounds the electrophilic
character of the vinylidene ligand is not significant. In
addition, it should be noted that the excess of amine or
the displaced phosphine does not deprotonate the
coordinated imine ligands of 5 and 6, indicating that
the pKa of this group depends not only on the substit-
uents of the imine but also on the co-ligands of the
complex.
The displacement of a triisopropylphosphine ligand
in 1 and 2 by allylamine is surprising, due to the soft
nature of the phosphine and osmium atom and the hard
nature of the amine, and in view of the known sentences
soft coordinates to soft and hard coordinates to hard. In
the search for some clue that will allow us to understand
the stability of 5 and 6, we carried out an X-ray
diffraction experiment on a single crystal of 5. A view
of the molecular geometry of this complex is shown in
Figure 3. Selected bond distances and angles are listed
in Table 2.
The geometry around the osmium atom can be
rationalized as a distorted octahedron with the nitrogen
atom of the allylamine ligand [N(2)] and the phosphorus
atom of triisopropylphosphine in trans positions [P-Os-
N(2) ) 176.08(19)°]. The perpendicular plane is formed
by the chloride ligands mutually cis disposed [Cl(1)-
Os-Cl(2) ) 84.35(6)°] and the nitrogen atom of the
imine [N(1)] and the CR atom [C(1)] of the vinylidene
also in cis position [N(1)-Os-C(1) ) 99.3(3)°].
The vinylidene ligand is bound to the metal in a
nearly linear fashion with an Os-C(1)-C(2) angle of
177.5(6)°. The Os-C(1) [1.812(7) Å] and C(1)-C(2)
[1.316(10) Å] distances are similar to the related pa-
rameters previously mentioned for 3.
dichlorometane-d2 solutions of 2 with 1.0 equiv of
diallylamine gives a 3:2 equilibrium mixture of 2 and
4. These molar ratios and those previously mentioned
indicate that the pKa of the coordinated imine of 2 is
lower than that of the coordinated imine of 1.
(iii) Allyla m in e. Although the pKa of allylamine (9.7)
is similar to those of triethylamine and diallylamine,
the behavior of 1 and 2 in the presence of this amine is
significantly different of that previously mentioned for
the other amines. In contrast to triethylamine and
diallylamine, the addition at room temperature of 1.0
equiv of allylamine to dichlorometane-d2 solutions of 1
leads to equilibrium mixtures of 1 (22%), 3 (8%), PiPr3
(35%), and the mixed amine-phosphine complex OsCl2-
(dCdCHPh){NHdC(CH3)2}(NH2CH2CHdCH2)(PiPr3) (5;
1
35%), according to the H and 31P{1H} NMR spectra of
the mixture. Similarly, the treatment at room temper-
ature of dichloromethame-d2 solutions of 2 with 1.0
equiv of allylamine affords equilibrium mixtures of 2
(9%), 4 (11%), PiPr3 (40%), and OsCl2(dCdCHPh){NHd
C(CH2)4CH2}(NH2CH2CHdCH2)(PiPr3) (6; 40%) (Scheme
2). In both cases, the addition of a second equivalent of
allylamine to the above-mentioned solutions produces
the shift of the equilibria toward the formation of 5 and
6, which are isolated as orange solids in high yield
(about 87%), by stirring at room temperature dichlo-
rometane solutions of 1 and 2 in the presence of 1.5
equiv of allylamine for 4 h.
Figure 2 shows, as a function of the time, the 31P-
{1H} NMR spectrum of the dichloromethane-d2 solution
of 1 with 2.0 equiv of allylamine. Initially the deproto-
nation of the imine occurs and complex 3 is formed.
However, the amount of 3 decreases by increasing the
reaction time. This decrease is accompanied with the
formation of 5 and free phosphine. According to Figure
2, complex 3 is the product of kinetic control in the
reaction of 1 with allylamine, whereas complex 5 is the
product of thermodynamic control.
The imine ligand is bound to the osmium atom in a
bent fashion, with a Os-N(1)-C(9) angle of 141.8(6)°,
which compares well with the Os-N-C angle found
in 1 [142.5(6)°], in [OsCl(dCdCHPh){NHdC(CH3)2}-
(H2O)(PiPr3)2][CF3SO3] [142.7(6)°],16 and in the rhenium
complex [Re(η5-C5H5)(NO)(NHdCPh2)(PPh3)] [136.2-
(3)°].11l The Os-N(1) bond length [2.052(6) Å] supports
the Os-N single bond formulation. It is statistically
identical with the Os-N bond length found in 1 [2.072-
(7) Å] and in the above-mentioned cationic-osmium
compound [2.067(5) Å],16 and about 0.2 Å longer than
that found in 3. The N(1)-C(9) [1.279(9) Å] distance is
similar to those observed in other imine transition metal
complexes,11 azavinylidene compounds,15,22,23 organic
azaallenium cations,25 and 2-azaallenyl complexes.26
Because evidence for the dissociation of triisopropy-
lphosphine from 1 has not been found, we have carried
out the reaction of 3 with [H3NCH2CHdCH2]Cl in the
presence and in the absence of NaCl, to know how the
substitution of phosphine by amine occurs. The addition
in an NMR tube of 1.0 equiv of [H3NCH2CHdCH2]Cl
to a dichloromethane-d2 solution of 3 leads after 10 min
to a 7:2 mixture of 5 and 1 plus free triisopropylphos-
phine, while the addition of 1.0 equiv of [H3NCH2CHd
At 173 K, the hydrogen atoms bonded to the nitrogen
atoms of the imine [H(02)] and amine [H(03) and H(04)]
ligands were located in the difference Fourier maps and
refined as isotropic atoms together with the rest of the

Reactivity of Imine-Vinylidene Complexes
Organometallics, Vol. 20, No. 8, 2001 1549
F igu r e 2. 31P{1H} NMR spectrum as a function of the time of the reaction of 1 with 2 equiv of allylamine.
Sch em e 3
non-hydrogen atoms of the structure, giving N(1)-
H(02), N(2)-H(03), and N(2)-H(04) distances of 0.88-
(8), 0.80(6), and 0.80(6) Å, respectively. Interestingly,
the separations between the H(02) hydrogen atom of the
imine and the chlorine ligand Cl(2) [2.58(7) Å] and the
H(03) hydrogen atom of the amine and the chlorine
ligand Cl(1) [2.59(8) Å] are shorter than the sum of the
van der Waals radii of hydrogen and chlorine [rvdw(H)
) 1.20, rvdw(Cl) ) 1.80 Å], suggesting that there are
intramolecular Cl‚‚‚H-N hydrogen bonds between these
atoms.27 The interactions give rise to four-membered
Os-Cl---H-N rings. An extended view of the structure
(Figure 4) indicates also short intermolecular interac-
tions [2.52(7) Å] between the H(04) hydrogen atoms of
the amines and the chlorine ligands Cl(2) of two
adjacent molecules in the crystal. Of great importance
in biological and organic chemistry,28 the hydrogen
(25) J ochims, J . C.; Abu-El-Halawa, R.; J ibril, I.; Huttner, G. Chem.
Ber. 1984, 117, 1900. (b) Al-Talib, M.; J ochims, J . C. Chem. Ber. 1984,
117, 3222. (c) Al-Talib, M.; J ibril, I.; Wu¨rthwein, E.-U.; J ochims, J . C.;
Huttner, G. Chem. Ber. 1984, 117, 3365. (d) Kupfer, R.; Wu¨rthwein,
E.-U.; Nagel, M.; Allmann, R. Chem. Ber. 1985, 118, 643. (e) Al-Talib,
M.; J ibril, I.; Huttner, G.; J ochims, J . C. Chem. Ber. 1985, 118, 1876.
(f) Al-Talib, M.; J ochims, J . C.; Zsolnai, L.; Huttner, G. Chem. Ber.
1985, 118, 1887. (g) Wu¨rthwein, E.-U.; Kupfer, R.; Allmann, R.; Nagel,
M. Chem. Ber. 1985, 118, 3632. (h) Krestel, M.; Kupfer, R.; Wu¨rthwein,
E.-U. Chem. Ber. 1987, 120, 1271.
(27) Analysis of the hydrogen bonds was made over all hydrogens
bonded to electronegative elements present in the structure and for
(26) Seitz, F.; Fischer, H.; Riede, J . J . Organomet. Chem. 1985, 287,
87. (b) Aumann, R.; Althaus, S.; Kru¨ger, S.; Betz, P. Chem. Ber. 1989,
122, 357. (c) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A.
M.; On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
which Distance(H‚‚‚Aacceptor-atom) < r(A, N ) 0.7) + 2.0 Å and
Angle(Ddonor-atom - H‚‚‚Aacceptor-atom) > 110°.
(28) J effrey, G. A.; Saenger, W. Hydrogen Bonding in Biological
Structures; Springer: Berlin, 1991.

1550 Organometallics, Vol. 20, No. 8, 2001
Castarlenas et al.
F igu r e 4. Intra- and intermolecular Os-Cl‚‚‚H-N inter-
actions in OsCl2(dCdCHPh)(NHdCMe2)(NH2CH2CHd
CH2)(PiPr3) (5).
two resonances, masked with that due to the CH2 group,
between 4.0 and 3.5 ppm. The resonances due to the
dCH proton of the vinylidene are observed at 2.18 (5)
and 2.25 (6) ppm as doublets with coupling constants
of 2.0 Hz. In the 13C{1H} NMR spectra, the CR atom of
the vinylidene gives rise to doublets at about 296 ppm
with C-P coupling constants of about 11 Hz, and the
Câ atom displays singlets at about 113 ppm. The
resonances corresponding to the CdN carbon atom of
the imines are observed at 181.4 (5) and 187.5 (6) ppm,
as singlets. The 31P{1H} NMR spectra contain singlets
at about -4.5 ppm.
F igu r e 3. Molecular diagram for OsCl2(dCdCHPh)-
(NHdCMe2)(NH2CH2CHdCH2)(PiPr3) (5). Thermal ellip-
soids are shown at 50% probability.
Ta ble 2. Selcted Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex OsCl2(dCdCHP h )-
(NHdCMe2)(NH2CH2CHdCH2)(P iP r 3) (5)
Os-C(1)
Os-N(1)
Os-N(2)
Os-P
Os-Cl(1)
C(1)-C(2)
1.812(7)
2.052(6)
2.186(6)
2.3507(18)
2.3938(17)
1.316(10)
C(2)-H(01)
N(1)-C(9)
N(1)-H(02)
N(2)-C(12)
N(2)-H(03)
N(2)-H(04)
0.92(7)
1.279(9)
0.88(8)
1.484(11)
0.80(6)
0.79(6)
(iv) An ilin e. The generality of the substitution of a
phosphine in 1 and 2 by primary amines is evident in
the synthesis of OsCl2(dCdCHPh)(NHdCR2)(NH2Ph)-
C(1)-Os-Cl(1)
C(1)-Os-Cl(2)
C(1)-Os-P
C(1)-Os-N(1)
C(1)-Os-N(2)
Cl(1)-Os-Cl(2)
Cl(1)-Os-P
Cl(1)-Os-N(1)
Cl(1)-Os-N(2)
97.0(2)
176.5(2)
89.2(2)
99.3(3)
94.4(3)
84.35(6)
97.10(6)
159.62(19)
80.8(2)
Cl(2)-Os-P
93.88(6)
78.67(19)
82.65(19)
95.24(17)
176.08(19)
85.9(3)
177.5(6)
141.8(6)
119.8(5)
Cl(2)-Os-N(1)
Cl(2)-Os-N(2)
P-Os-N(1)
(PiPr3) [CR2 ) CMe2 (7), C(CH2)4CH2 (8)]. These com-
pounds are prepared, similarly to 5 and 6, by addition
at room temperature of 1.5 equiv of aniline to dichlo-
romethane solutions of 1 and 2, respectively (eq 2).
P-Os-N(2)
N(1)-Os-N(2)
Os-C(1)-C(2)
Os-N(1)-C(9)
Os-N(2)-C(12)
hydrogen bonds
D(H-acceptor atom) A(donor atom-H‚‚‚acceptor atom)
N(1)-H(02)‚‚‚Cl(2)
N(2)-H(03)‚‚‚Cl(1)
N(2)-H(04)‚‚‚Cl(2)
(-x+2, -y+1, -z+1)
2.58(7)
2.59(8)
2.52(7)
104(6)
110(7)
162(6)
Complexes 7 and 8 were isolated as orange solids in
high yield (about 80%) and characterized by MS,
bonding is presently attracting considerable interest in
the chemistry of transition metals.16,29
Are the interactions H(03)‚‚‚Cl(1) and H(04)‚‚‚Cl(2)
the reason for the formation of 5? We cannot assure this
but the fact is that, although one should expect that the
stabilization achieved by means of the H‚‚‚Cl interac-
tions is small, it may be enough. Furthermore, it should
be noted that triethylamine and even diallylamine do
not afford compounds related to 5 and 6.
In agreement with the presence of the imine and
amine ligands in 5 and 6, the IR spectra in KBr of these
compounds contain three ν(N-H) bands between 3300
and 3100 cm-1. In addition, the spectra show ν(CdN)
and ν(OsdCdC) absorptions at about 1660 and 1610
cm-1, respectively. In the 1H NMR spectra the reso-
nances corresponding to the NH-hydrogen atom of the
imines appear at about 10.6 ppm, as broad signals,
whereas the NH-hydrogen atoms of the amine display
(29) Stevens, R. C.; Bau, R.; Milstein, D.; Blum, O.; Koetzle, T. F.
J . Chem. Soc., Dalton Trans. 1990, 1429. (b) Lough, A. J .; Park, S.;
Ramachandran, R.; Morris, R. H. J . Am. Chem. Soc. 1994, 116, 8356.
(c) Shubina, E. S.; Belkova, N. V.; Krilov, A. N.; Vorontsov, E. V.;
Epstein, L. M.; Gusev, D. G.; Niedermann, M.; Berke, H. J . Am. Chem.
Soc. 1996, 118, 1105. (d) Braga, D.; Grepioni, F.; Desiraju, G. R. J .
Organomet. Chem. 1997, 548, 33. (e) Ayllon, J . A.; Sabo-Etienne, S.;
Chaudret, B.; Ulrich, S.; Limbad, H.-H. Inorg. Chim. Acta 1997, 259,
1. (f) Aime, S.; Gobetto, R.; Valls, E. Organometallics 1997, 16, 5140.
(g) Crabtree, R. H.; Eisenstein, O.; Sini, G.; Peris, E. J . Organomet.
Chem. 1998, 567, 7. (h) Crabtree, R. H. J . Organomet. Chem. 1998,
577, 111. (i) Yandulov, D. V.; Caulton, K. G.; Belkova, N. V.; Shubina,
E. S., Epstein, L. M.; Khoroshun, D. V.; Musaev, D. G.; Morokuma, K.
J . Am. Chem. Soc. 1998, 120, 12553. (j) Gusev, D. G.; Lough, A. J .;
Morris, R. H. J . Am. Chem. Soc. 1998, 120, 13138. (k) Buil, M. L.;
Esteruelas, M. A.; On˜ate, E.; Ruiz, N. Organometallics 1998, 17, 3346.
(l) Lee, D.-H.; Kwon, H. J .; Patel, B. P.; Liable-Sands, L. M.; Rheingold,
A. L.; Crabtree, R. H. Organometallics 1999, 18, 1615. (m) Esteruelas,
M. A.; Oliva´n, M.; On˜ate, E.; Ruiz, N.; Tajada, M. A. Organometallics
1999, 18, 2953. (n) Esteruelas, M. A.; Gutie´rrez-Puebla, E.; Lo´pez, A.
M.; On˜ate, E.; Tolosa, J . I. Organometallics 2000, 19, 275.

Reactivity of Imine-Vinylidene Complexes
Organometallics, Vol. 20, No. 8, 2001 1551
elemental analysis, IR, and 1H, 13C{1H}, and 31P{1H}
NMR spectroscopy. As in the IR spectra of 5 and 6, the
IR spectra of 7 and 8 contain three ν(N-H) bands
between 3300 and 3100 cm-1 along with the ν(CdN) and
appear at 3271 (9) and 3254 (10) cm-1. In addition the
spectra show ν(CdN) bands at 1637 (9) and 1621 (10)
cm-1 and the absorptions due to the [BF4]- anions with
Td symmetry, centered at 1053 (9) and 1061 (10) cm-1
.
ν(OsdCdC) absorptions at about 1660 and 1610 cm-1
,
In the solid state, these compounds are stable for one
month if kept under argon at -20 °C. At this temper-
ature, in dichloromethane solutions, they are stable for
a few hours. In the 1H NMR spectra of 9 and 10 in
dichloromethane-d2 at -40 °C, the most noticeable
resonances are broad signals at about 9.8 ppm corre-
sponding to the NH proton of the imines and broad
singlets at about 3.8 ppm, due to the CH2 protons of
the carbyne. In the 13C{1H} NMR spectra at -40 °C,
the CR resonances of the carbyne appear at about 282
ppm as triplets with C-P coupling constants of about
9 Hz, whereas the Câ resonances are observed at about
61 ppm as singlets. The CdN carbon atoms of the imines
display singlets at 188.1 (9) and 192.3 (10) ppm. The
31P{1H} NMR spectra contain singlets at about 5 ppm.
3. F or m a tion of OsCl2(dCdCHP h )(P iP r 3)2. Ru-
thenium vinylidene complexes of the type RuCl2(dCd
CHR)(PR′3)2 have been known since 1991.30 Since the
advent of Grubbs ROMP catalysts RuCl2(dCR2)(PR′3)2,31
the synthesis of this type of vinylidene derivatives has
experienced an increased interest.32 However, pathways
for the preparation of the osmium counterparts have
not been found, although their search has been in-
tense.17
respectively. In the 1H NMR spectra, the resonances
corresponding to the NH-hydrogen atom of the imines
appear at about 10.6 ppm, whereas the NH-hydrogen
atoms of the aniline display two resonances between 5.8
and 5.5 ppm. For both compounds, the resonance due
to the dCH hydrogen atom of the vinylidene group is
observed at about 2.1 ppm, as a doublet with a H-P
coupling constant of about 1.5 Hz. The 13C{1H} NMR
spectra agree well with those of 5 and 6; the CR atom of
the vinylidene displays at about 297 ppm doublets with
C-P coupling constants of about 11 Hz, whereas the
resonances due to the Câ atom are observed at about
115 ppm as singlets. The resonances corresponding to
the CdN carbon atom of the imines appear at about 182
ppm, as singlets. The 31P{1H} NMR spectra show
singlets at about -1 ppm.
2. Rea ction s of 1 a n d 2 w ith HBF 4. Equation 1 and
Scheme 2 show that complexes 1 and 2 have typical
behavior of a Bro¨nsted acid, transferring one proton to
bases such as nBuLi and amines. Although, at first
glance, these compounds could have two electrophilic
hydrogen atoms, the NH of the imines and dCH of the
vinylidene, only one of them is transferred, that of the
imine ligands. This fact, together with the inertia of the
vinylidene toward the addition of primary amines,
suggests that the vinylidene is a nucleophile, and
therefore, compounds 1 and 2 should also shown Bro¨n-
sted base behavior, accepting a proton of strong acids.
To corroborate this, we have also carried out the
reactions of 1 and 2 with HBF4.
Complexes
1 and 2 are precursors of OsCl2-
(dCdCHPh)(PiPr3)2 (11), in agreement with the weak
Lewis basicity of the imine nitrogen atom.33 The heating
of toluene solutions of these compounds under reflux
for 24 h affords purple solutions, from which complex
11 is isolated as a purple solid in about 60% yield (eq
4). The formation of 11 is probably favored by the low
stability of the free aliphatic N-H ketimines, which in
the presence of traces of water evolve into ketones.34
The addition at room temperature of 1.0 equiv of
HBF4‚OEt2 to diethyl ether solutions of 1 and 2 leads
to the immediate formation of the carbyne-imine
derivatives [OsCl2(tCCH2Ph)(NHdCR2)(PiPr3)2][BF4]
[CR2 ) CMe2 (9), C(CH2)4CH2 (10)], as a result of the
addition of the proton from the acid to the Câ atom of
the vinylidene (eq 3). The regioselectivity of the addition
is in agreement with the previously mentioned theoreti-
cal studies on vinylidene compounds, which have identi-
fied the localization of the electron density on the Câ
atom.1
In the IR spectrum of 11 in KBr, the most noticeable
features are the absence of any ν(NH) band and the
presence of the ν(OsdCdC) vibration corresponding to
(30) Wakatsuki, Y.; Yamazaki, H.; Kumegawa, N.; Satoh, T.; Satoh,
J . Y. J . Am. Chem. Soc. 1991, 113, 9604. (b) Wakatsuki, Y.; Koga, N.;
Yamazaki, H.; Morokuma, K. J . Am. Chem. Soc. 1994, 116, 8105.
(31) Nguyen, S. T.; J ohnson, L. K.; Grubbs, R. H.; Ziller, J . W. J .
Am. Chem. Soc. 1992, 114, 3974. (b) Nguyen, S. T.; Grubbs, R. H.;
Ziller, J . W. J . Am. Chem. Soc. 1993, 115, 9858. (c) Kanaoka, S.;
Grubbs, R. H. Macromolecules 1995, 28, 4707. (e) Hillmyer, M. A.;
Laredo, W. R.; Grubbs, R. H. Macromolecules 1995, 28, 6311. (f)
Nguyen, S. T.; Grubbs, R. H. J . Organomet. Chem. 1995, 497, 195. (g)
Belderrein, T. R.; Grubbs, R. H. Organometallics 1997, 16, 4001. (i)
Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J . Am. Chem. Soc. 1997, 119,
3887. (j) Weck, M.; J ackiw, J . J .; Rossi, R. R.; Weiss, P. S.; Grubbs, R.
H. J . Am. Chem. Soc. 1999, 121, 4088.
(32) Gru¨nwald, C.; Gevert, O.; Wolf, J .; Gonzalez-Herrero, P.;
Werner, H. Organometallics 1996, 15, 1960. (b) Schwab, P.; Grubbs,
R. H.; Ziller, J . W. J . Am. Chem. Soc. 1996, 118, 100. (c) Wolf, J .; Stu¨er,
W.; Gru¨nwald, C.; Gevert, O.; Laubender, M.; Werner, H. Eur. J . Inorg.
Chem. 1998, 1827. (d) Katayama, H.; Ozawa, F. Organometallics 1998,
17, 5190. (e) Katayama, H.; Ozawa, F. Chem. Lett. 1998, 67.
(33) Mehrota, R. C. In Comprehensive Coordination Chemistry;
Wilkinson, G.; Gillard, R. D.; McCleverty, J . A., Ed.; Pergamon: Oxford,
England, 1987; Vol. 2, pp 269-287.
The reactions shown in eq 3 are reversible. Thus, the
addition of 1.0 equiv of triethylamine to dichloromethane-
d2 solutions of 9 and 10 regenerates 1 and 2, respec-
tively. The selectivity of these deprotonations agrees
well with the high stability of 1 and 2, which do not
evolve into azavinylidene-carbyne species by hydrogen
transfer from the imines to the vinylidene group.
Complexes 9 and 10 were isolated as yellow solids in
high yield (about 85%). In the IR spectra in KBr, the
ν(NH) absorptions of the coordinated imine groups

1552 Organometallics, Vol. 20, No. 8, 2001
Castarlenas et al.
the vinylidene ligand at 1611 cm-1. In the 1H NMR
spectrum in benzene-d6, the resonance due to the CHd
vinylidene proton is observed at 2.14 ppm, as a triplet
with a H-P coupling constant of 2.7 Hz. In the 13C{1H}
spectrum the CR atom of the vinylidene gives rise at
278.9 ppm to a triplet with a C-P coupling constant of
9.6 Hz, and the Câ atom displays at 110 ppm another
triplet but with a C-P coupling constant of 4.0 Hz. The
31P{1H} NMR spectrum shows a singlet at 5.5 ppm.
These spectroscopic data agree well with those previ-
ously reported for the ruthenium counterpart, where the
square-pyramidal structure has been proven by X-ray
diffraction analysis.32c,d
usual procedures and distilled under argon prior to use. The
starting materials, OsCl2(dCdCHPh){NHdC(CH3)2}(PiPr3)2
(1) and OsCl2(dCdCHPh){NHdC(CH2)4CH2}(PiPr3)2 (2), were
prepared by the published method.16 1H NMR spectra were
recorded at 300 MHz, and chemical shifts are expressed in
ppm downfield from Me4Si. 13C{1H} NMR spectra were re-
corded at 75.4 MHz, and chemical shifts are expressed in ppm
downfield from Me4Si. 31P{1H}NMR spectra were recorded at
121.4 MHz, and chemical shifts are expressed in ppm down-
field from 85% H3PO4. Coupling constants, J and N, are given
in hertz.
Rea ction of 1 w ith Tr ieth yla m in e. A solution of 1 (13
mg, 0.018 mmol) in 0.5 mL of dichloromethane-d2 in an NMR
tube was treated with triethylamine (2.5 µL, 0.018 mmol). The
NMR tube was sealed under argon, and after 10 min 1H and
31P{1H} NMR measurements were made. An 1:5 equilibrium
mixture of 1 and 3 was obtained.
Con clu d in g Rem a r k s
This study has revealed that the reactivity of imine-
vinylidene compounds of the type OsCl2(dCdCHPh)-
(NHdCR2)(PiPr3)2 is the result of (i) the electrophilic
character of the NH-hydrogen atom of the imine and
the nucleophilic character of the vinylidene ligand, (ii)
the electronegativity of the chlorine ligands, which favor
the formation of hydrogen bonds, and (iii) the weak
Lewis basicity of the imine nitrogen atom.
As a consequence of the electrophilic character of the
NH-hydrogen atom of the imine and the nucleophilic
character of the vinylidene, these compounds have
amphoteric nature, transferring the NH-hydrogen pro-
ton to bases such as amines and nBuLi and accepting
the proton from HBF4. In their reactions as acids, the
conjugated bases are the five-coordinate azavinylidene-
vinylidene compounds OsCl(dNdCR2)(dCdCHPh)(Pi-
Pr3)2, which coordinate the azavinylidene ligands in a
bent fashion. In their reactions as bases, the conjugated
acids are the carbyne-imine derivatives [OsCl2(tCCH2-
Ph)(NHdCR2)(PiPr3)2]+.
The high electronegativity of the chlorine does makes
this ligand efficient for forming inter- and intramolecu-
lar hydrogen bonds with ligands containing hydrogen
atoms bonded to the donor atom. The additional stabi-
lization resulting from these H‚‚‚Cl interactions appears
to be the reason for the surprising formation of the
mixed amine-phosphine complexes OsCl2(dCdCHPh)-
(NHdCR2)(NH2R′)(PiPr3), which are obtained as a result
of the displacement of a triisopropylphosphine ligand
from OsCl2(dCdCHPh)(NHdCR2)(PiPr3)2 by primary
amines.
As a result of the weak Lewis basicity of the nitrogen
atom of the imines, complexes OsCl2(dCdCHPh)(NHd
CR2)(PiPr3)2 dissociate the N-H ketimine in toluene
under reflux, to give OsCl2(dCdCHPh)(PiPr3)2. The
driving force of this reaction could be the low stability
of the free aliphatic N-H ketimines.
Rea ction of 2 w ith Tr ieth yla m in e. A solution of 2 (13
mg, 0.018 mmol) in 0.5 mL of dichloromethane-d2 in an NMR
tube was treated with triethylamine (2.5 µL, 0.018 mmol). The
NMR tube was sealed under argon, and after 10 min 1H and
31P{1H} NMR measurements were made. An 1:9 equilibrium
mixture of 2 and 4 was obtained.
Rea ction of 1 w ith n Bu Li: P r ep a r a tion of OsCl{dNd
C(CH3)2}(dCdCHP h )(P iP r 3)2 (3). An orange solution of 1
(100 mg, 0.134 mmol) in 10 mL of THF was treated with
nBuLi (60 µL, 0.150 mmol, 2.5 M in hexanes). After 10 min,
n
0.5 mL of 2-propanol was added to eliminate the excess BuLi.
Then, the solvent was removed and dichloromethane (10 mL)
was added to filter the ionic salts. The resulting orange
solution was evaporated to dryness, and addition of methanol
(2 mL) yielded an orange solid that was washed with methanol
(2 × 2 mL) and dried in vacuo. Yield: 75 mg (79%). Anal. Calcd
for C29H54NClOsP2: C, 49.45; H, 7.73; N, 1.99. Found: C,
49.15; H, 7.58; N, 1.83. IR (KBr, cm-1): ν(CdN) 1671 (m); ν-
(OsdCdC) 1608 (s). 1H NMR (C6D6, 20 °C): δ 7.3-7.2 (m, 4H,
H
Ph); 6.85 (t, J H-H ) 6.5, 1H, Hpara-Ph); 3.40 (t, J H-P ) 2.1, 1H,
OsdCdCHPh); 2.71 (m, 6H, PCH); 2.17 and 1.98 (both s, 6H,
{CH3}2CdN); 1.35 and 1.13 (both dvt, J H-H ) 6.9, N ) 13.5,
36H, PCHCH3). 13C{1H} NMR plus DEPT (C6D6, 20 °C): δ
275.0 (t, J C-P ) 11.2, OsdC); 153.8 (t, J C-P ) 3.2, CdN); 135.5
(t, J C-P ) 2.3, Cipso-Ph); 128.1, 124.0, and 122.5 (all s, CPh); 113.2
(t, J C-P ) 3.9, OsdCdC); 22.9 (vt, N ) 22.8, PCH); 19.7 and
19.3 (both s, PCHCH3); 19.5 and 19.2 (both s, {CH3}2CdN).
31P{1H} NMR (C6D6, 20 °C): δ 4.2 (s). MS (FAB+): m/z 705
(M+).
Rea ction of 2 w ith n Bu li: P r ep a r a tion of OsCl{dNd
C(CH2)4CH2}(dCdCHP h )(P iP r 3)2 (4). This complex was
prepared as described for 3 starting from 100 mg (0.128 mmol)
of 2 and nBuLi (55 µL, 0.137 mmol, 2.5 M in hexanes). Yield:
75 mg (78%). Anal. Calcd for C32H58NClOsP2: C, 51.63; H, 7.85;
N, 1.88. Found: C, 51.53; H, 7.79; N, 1.78. IR (KBr, cm-1):
ν(CdN) 1655 (m); ν(OsdCdC) 1605 (s). 1H NMR (C6D6, 20
°C): δ 7.31 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 7.27 (d, J H-H ) 7.8,
2H, Hortho-Ph); 6.85 (t, J H-H ) 6.9, 1H, Hpara-Ph); 3.41 (t, J H-P
) 3.0, 1H, OsdCdCHPh); 2.76 (m, 6H, PCH); 2.62 and 2.29
In conclusion, complexes OsCl2(dCdCHPh)(NHd
CR2)(PiPr3)2 are electrophiles at the NH-hydrogen atom
and nucleophiles at the Câ atom of the vinylidene group.
They exchange a phosphine ligand by primary amines
and lose the imine ligand in toluene under reflux.
(both m, 4H, {CH2}2CdN); 1.38 and 1.15 (both dvt, J H-H
)
6.9, N ) 13.5, 36H, PCHCH3) 1.4-1.2 (m, 6H, Cy). 13C{1H}
NMR plus APT (C6D6, 20 °C): δ 275.0 (t, J C-P ) 10.9, OsdC);
158.2 (t, J C-P ) 2.0, CdN); 135.3 (s, Cipso-Ph); 127.4, 123.4, and
121.3 (all s, CPh); 112.6 (t, J C-P ) 2.5, OsdC)C); 33.1, 32.7,
26.7, and 25.2 (all s, CH2 Cy); 22.4 (vt, N ) 22.9, PCH); 19.4
and 19.3 (both s, PCHCH3). 31P{1H} NMR (C6D6, 20 °C): δ 4.2
(s). MS (FAB+): m/z 745 (M+).
Exp er im en ta l Section
All reactions were carried out with rigorous exclusion of air
using Schlenk-tube techniques. Solvents were dried by the
Rea ction of 1 w ith Dia llyla m in e. A solution of 1 (15 mg,
0.020 mmol) in 0.5 mL of dichloromethane-d2 in an NMR tube
was treated with diallylamine (2.5 µL, 0.020 mmol). The NMR
tube was sealed under argon, and after 10 min 1H and 31P-
{1H} NMR measurements were made. A 2:1 equilibrium
mixture of 1 and 3 was obtained.
(34) March, J . Advanced Organic Chemistry: Reactions, Mechanisms,
and Structure; McGraw-Hill Book Co.: New York, 1968; Chapter 16,
p 656. (b) Robertson, G. M. In Comprehensive Organic Functional
Group Transformations; Katritzley, A. R., Meth-Cohn, O., Rees, C. W.,
Eds.; Pergamon: Oxford, England, 1995; Vol. 3, pp 403-432.

Reactivity of Imine-Vinylidene Complexes
Organometallics, Vol. 20, No. 8, 2001 1553
Rea ction of 2 w ith Dia llyla m in e. A solution of 2 (15 mg,
0.019 mmol) in 0.5 mL of dichloromethane-d2 in an NMR tube
was treated with diallylamine (2.5 µL, 0.020 mmol). The NMR
tube was sealed under argon, and after 10 min 1H and 31P-
{1H} NMR measurements were made. A 3:2 equilibrium
mixture of 2 and 4 was obtained.
equilibrium mixture of 5 and 1 plus free triisopropylphosphine
was obtained.
Rea ction of 3 w ith [H3NCH2CHdCH2]Cl in th e P r es-
en ce of Na Cl. A solution of 3 (15 mg, 0.021 mmol) in 0.5 mL
of acetone-d6 in an NMR tube was treated with [H3NCH2CHd
CH2]Cl (2 mg, 0.021 mmol) and NaCl (10 mg, 0.170 mmol).
The NMR tube was sealed under argon, and after 10 min 1H
and 31P{1H} NMR measurements were made. A 1:4 equilib-
rium mixture of 5 and 1 plus free triisopropylphosphine was
obtained.
Rea ction of 1 w ith Allyla m in e. A solution of 1 (15 mg,
0.020 mmol) in 0.5 mL of dichloromethane-d2 in an NMR tube
was treated with allylamine (1.5 µL, 0.020 mmol). The NMR
tube was sealed under argon, and after 6 h 1H and 31P{1H}
NMR measurements were made. An equilibrium mixture of 1
(22%), 3 (8%), PiPr3 (35%), and 5 (35%) was obtained.
P r ep a r a tion
of OsCl2{dCdCHP h ){NHdC(CH3)2}-
(NH2P h )(P iP r 3) (7). An orange solution of 1 in dichlo-
romethane (100 mg, 0.135 mmol) was treated with aniline (18
µL, 0.197 mmol). After stirring for 36 h at room temperature
the solvent was removed to dryness. Addition of pentane
caused the precipitation of an orange solid that was washed
(4 × 3 mL) with pentane and dried in vacuo. Yield: 75 mg
(83%). Anal. Calcd for C26H41N2Cl2OsP: C, 46.35; H, 6.13; N,
4.16. Found: C, 46.42; H, 6.28; N, 3.94. IR (KBr, cm-1): ν-
(N-H) 3224 (m) and 3158 (m); ν(CdN) 1655 (m); ν(OsdCdC)
1613 (s). 1H NMR (C6D6, 20 °C): δ 10.57 (s, 1H, CdN-H); 7.5-
6.8 (m, 10H, HPh); 5.8 and 5.5 (both m, 2H, NH2); 2.68 (m, 3H,
PCH); 2.08 (d, J H-H ) 1.8, 1H, OsdCdCHPh); 1.53 and 1.09
(both s, 6H, {CH3}2CdN); 1.20 (m, 18H, PCHCH3). 13C{1H}
NMR plus APT (acetone-d6, 20 °C): δ 297.4 (d, J C-P ) 11.0,
OsdC); 180.4 (s, CdN); 142.1 (s, N-CPh); 130.4 (s, Cipso-Ph);
128.6, 125.9, 124.0, and 121.4 (all s, CPh); 114.5 (s, OsdCdC);
30.2 and 22.8 (both s,{CH3}2CdN); 30.0 (s, CH2Ph); 26.6 (d,
J C-P ) 28.0, PCH); 19.5 and 19.3 (both s, PCHCH3). 31P{1H}
Rea ction of 2 w ith Allyla m in e. A solution of 2 (15 mg,
0.020 mmol) in 0.5 mL of dichloromethane-d2 in an NMR tube
was treated with allylamine (1.5 µL, 0.020 mmol). The NMR
tube was sealed under argon, and after 6 h 1H and 31P{1H}
NMR measurements were made. An equilibrium mixture of 2
(9%), 4 (11%), PiPr3 (40%), and 6 (40%) was obtained.
P r ep a r a tion
of
OsCl2(dCdCHP h ){NHdC(CH3)2}-
(NH2CH2CHdCH2)(P iP r 3) (5). An orange solution of 1 in
dichloromethane (100 mg, 0.135 mmol) was treated with
allylamine (15 µL, 0.200 mmol). After stirring for 4 h at room
temperature the solvent was removed to dryness. Addition of
pentane caused the precipitation of an orange solid that was
washed (4 × 3 mL) with pentane and dried in vacuo. Yield:
75 mg (87%). Anal. Calcd for C23H41N2Cl2OsP: C, 43.32; H,
6.48; N, 4.39. Found: C, 43.46; H, 6.53; N, 4.19. IR (KBr, cm-1):
ν(N-H) 3293 (m), 3206 (m), and 3125 (m); ν(CdN) 1660 (m);
1
ν(OsdCdC) 1617 (s). H NMR (acetone-d6, 20 °C): δ 10.61 (s,
NMR (C6D6, 20 °C): δ -1.1 (s). MS (FAB+): m/z 581 [M+
(NH2Ph)].
-
1H, CdN-H); 7.34 (d, J H-H ) 7.5, 2H, Hortho-Ph); 7.14 (t, J H-H
) 7.5, 2H, Hmeta-Ph); 6.65 (t, J H-H ) 7.5, 1H, Hpara-Ph); 5.7 (m,
1H, -CHdCH2); 4.85 (d, J H-H ) 17.1, -CHdCHtrans); 4.74 (d,
J H-H ) 10.2, -CHdCHcis); 3.9-3.5 (m, 4H, CH2 and NH2); 2.73
(m, 3H, PCH); 2.18 (d, J H-H ) 1.8 Hz, 1H, CdCHPh); 2.04
and 1.96 (both s, 6H, {CH3}2CdN); 1.19 (dd, J H-H ) 7.5, J H-P
) 6.3, 18H, PCHCH3). 13C{1H} NMR plus APT (acetone-d6,
20 °C): δ 296.1 (d, J C-P ) 10.6, OsdC); 181.4 (s, CdN); 137.4
(s, -CHd); 130.8 (s, Cipso-Ph); 127.3, 125.4, and 123.6 (both s,
P r ep a r a t ion
of
OsCl2(dCdCH P h )(NH2P h ){NH d
C(CH2)4CH2}(P iP r 3) (8). This complex was prepared as
described for 7 starting from 100 mg (0.128 mmol) of 2 and 18
µL (0.197 mmol) of aniline. Yield: 75 mg (82%). Anal. Calcd
for C29H45N2Cl2OsP: C, 48.80; H, 6.35; N, 3.92. Found: C,
48.95; H, 6.66; N, 3.63. IR (KBr, cm-1): ν(N-H) 3220 (m) and
3160 (m); ν(CdN) 1660 (m); ν(OsdCdC) 1615 (s). 1H NMR
(C6D6, 20 °C): δ 10.62 (s, 1H, CdN-H); 7.8-6.8 (m, 10H, HPh);
5.8 and 5.5 (both m, 2H, NH2); 2.67 (m, 3H, PCH); 2.14 (d,
J H-H ) 1.5, 1H, OsdCdCHPh); 1.8-0.7 (m, 10H, Cy); 1.2 (m,
18H, PCHCH3). 13C{1H} NMR plus APT (acetone-d6, 20 °C):
δ 296.8 (d, J C-P ) 11.5, OsdC); 184.6 (s, CdN); 142.3 (s,
N-CPh); 130.1 (s, Cipso-Ph); 128.7, 126.0, 124.4, 123.9, and 121.3
(all s, CPh); 114.6 (OsdCdC); 41.6, 32.8, 26.4, 25.4, and 24.2
(all s, CH2 Cy); 26.5 (d, J C-P ) 28.0, PCH); 19.4 and 19.1 (both
s, PCHCH3). 31P{1H} NMR (C6D6, 20 °C): δ -0.8 (s). MS
(FAB+): m/z 621 [M+ - (NH2Ph)].
P r ep a r a tion of [OsCl2(tC-CH2P h ){NHdC(CH3)2}-
(P iP r 3)2]BF 4 (9). An orange solution of 1 (100 mg, 0.135 mmol)
in 10 mL of diethyl ether was treated with tetrafluoroboric
acid (18 µL, 0.135 mmol, 54% in diethyl ether). A yellow solid
was formed immediately, and after 10 min of stirring, it was
washed with diethyl ether (2 × 3 mL) and dried in vacuo.
Yield: 95 mg (85%). Anal. Calcd for C29H56NBCl2F4OsP2: C,
42.04; H, 6.81; N, 1.69. Found: C, 42.33; H, 7.14; N, 1.77. IR
(KBr, cm-1): ν(N-H) 3271 (m); ν(CdN) 1637 (s); ν(BF4) 1053
(vs, br). 1H NMR (CD2Cl2, -40 °C): δ 9.82 (br, 1H, N-H); 7.4-
7.2 (m, 5H, Ph); 3.83 (s, 2H, CH2Ph); 2.68 (m, 6H, PCH); 2.58
(s, 6H, {CH3}2CdN); 1.28 (m, 36H, PCHCH3). 13C{1H} NMR
(CD2Cl2, -40 °C): δ 281.7 (t, J C-P ) 9.0, OstC); 188.1 (s, Cd
N); 129.5, 129.3, 128.6, and 127.2 (all s, CPh); 60.8 (s, CH2Ph);
31.8 and 26.6 (both s, {CH3}2CdN); 25.5 (vt, N ) 23.2, PCH);
19.7 (br, PCHCH3). 31P{1H} NMR (CD2Cl2, -40 °C): δ 4.0 (s).
MS (FAB+): m/z 742 (M+); 706 (M+ - HCl); 685 (M+ - HNd
C{CH3}2).
C
Ph); 116.5 (s, dCH2); 113.6 (s, OsdCdC); 46.9 (s, N-CH2);
30.5 and 24.1 (both s,{CH3}2CdN); 26.3 (d, J C-P ) 28.0, PCH);
19.5 and 19.2 (both s, PCHCH3). 31P{1H} NMR (acetone-d6,
20 °C): δ -4.6 (s). MS (FAB+): m/z 638 (M+), 602 (M+ - Cl)
and 581 [M+ - (NH2CH2CHdCH2)].
P r ep a r a tion of OsCl2(dCdCHP h ){NHdC(CH 2)4CH2}-
(NH2CH2CHdCH2)(P iP r 3) (6). This complex was prepared
as described for 5 starting from 100 mg (0.128 mmol) of 2 and
15 µL (0.200 mmol) of allylamine. Yield: 75 mg (86%). Anal.
Calcd for C26H45N2Cl2OsP: C, 46.08; H, 6.69; N, 4.13. Found:
C, 46.42; H, 6.73; N, 4.24. IR (KBr, cm-1): ν(N-H) 3290 (m),
3206 (m), and 3123 (m); ν(CdN) 1655 (m); ν(OsdCdC) 1610
(s). 1H NMR (acetone-d6, 20 °C): δ 10.58 (s, 1H, CdN-H); 7.23
(d, J H-H ) 7.5, 2H, Hortho-Ph); 7.13 (t, J H-H ) 7.5, 2H, Hmeta-Ph);
6.72 (t, J H-H ) 7.5, 1H, Hpara-Ph); 5.9 (m, 1H, -CHdCH2); 5.16
(d, J H-H ) 17.1, -CHdCHtrans); 5.09 (d, J H-H ) 10.2, -CHd
CHcis); 4.2-3.7 (m, 4H, CH2 and NH2); 2.82 (m, 3H, PCH); 2.25
(d, J H-P ) 2.0, 1H, CdCHPh); 2.0-1.4 (m, 10H, Cy); 1.38 (dd,
J H-H ) 7.5, J H-P ) 6.3, 18H, PCHCH3). 13C{1H} NMR plus
APT (acetone-d6, 20 °C): δ 295.8 (d, J C-P ) 11.9, OsdC); 187.5
(s, CdN); 137.1 (s, -CHd); 131.1 (s, Cipso-Ph); 128.0, 125.3, and
123.1 (all s, CPh); 116.5 (s, dCH2); 112.8 (s, OsdCdC); 46.8 (s,
N-CH2); 42.4, 34.1, 27.2, 26.7, and 24.8 (all s, CH2 Cy); 26.1
(d, J C-P ) 28.0, PCH); 19.5 and 19.2 (both s, PCHCH3). 31P-
{1H} NMR (acetone-d6, 20 °C): δ -4.0 (s). MS (FAB+): m/z
678 (M+), 642 (M+ - Cl) and 621 [M+ - (NH2CH2CHdCH2)].
Rea ction of 3 w ith [H3NCH2CHdCH2]Cl. A solution of
3 (15 mg, 0.021 mmol) in 0.5 mL of dichloromethane-d2 in an
NMR tube was treated with [H3NCH2CHdCH2]Cl (2 mg, 0.021
mmol). The NMR tube was sealed under argon, and after 10
min 1H and 31P{1H} NMR measurements were made. A 7:2
P r ep a r a tion of [OsCl2(tC-CH2P h ){NHdC(CH2)4CH2}-
(P iP r 3)2]BF 4 (10). This complex was prepared as described
for 9 starting from 100 mg (0.128 mmol) of 2 and tetrafluo-

1554 Organometallics, Vol. 20, No. 8, 2001
Castarlenas et al.
Ta ble 3. Cr ysta l Da ta a n d Da ta Collection a n d
Refin em en t for Com p lexes
roboric acid (17 µL, 0.128 mmol, 54% in diethyl ether). Yield:
95 mg (86%). Anal. Calcd for C32H60NBCl2F4OsP2: C, 44.25;
H, 6.96; N, 1.61. Found: C, 44.45; H, 7.31; N, 1.56. IR (KBr,
cm-1): ν(N-H) 3254 (m); ν(CdN) 1621 (s); ν(BF4) 1061 (vs,
br). 1H NMR (CD2Cl2, -40 °C): δ 9.84 (br, 1H, N-H); 7.4-7.2
(m, 5H, Ph); 3.86 (s, 2H, CH2Ph); 2.9-2.7 (m, 10H, PCH,
{CH2}2CdN); 1.73 and 1.58 (both m, 6H, Cy); 1.30 (m, 36H,
PCHCH3). 13C{1H} NMR plus DEPT (CD2Cl2, -40 °C): δ 281.9
(t, J C-P ) 8.6, OstC); 192.3 (s, CdN); 129.7, 129.4, and 128.7
(all s, CPh); 127.4 (s, Cipso-Ph); 61.2 (s, CH2Ph); 43.3, 36.1, 26.9,
26.2, and 22.8 (all s, CH2, Cy); 25.5 (br, PCH); 19.9 and 19.1
(both br, PCHCH3). 31P{1H} NMR (CD2Cl2, -40 °C): δ 4.8 (s).
MS (FAB+): m/z 782 (M+); 746 (M+ - HCl); 685 (M+ - NHd
OsCl(dNdCMe2)(dCdCHP h )(P iP r 3)2 (3) a n d
[OsCl2(dCdCHP h )(NHdCMe2)-
(NH2CH2CHdCH2)(P iP r 3) C7H8 (5)
3
5
formula
mol wt
C
29H54ClNOsP2
C23H41Cl2N2OsP C7H8
729.78
704.36
color and habit red block
red block
triclinic, P1h
9.4244(9)
10.6728(10)
16.6864(15)
81.515(2)
83.561(2)
82.244(2)
1637.5(3)
2
space group
a, Å
monoclinic, P21/m
9.4978(8)
b, Å
c, Å
13.0692(12)
13.5472(12)
R, deg
â, deg
γ, deg
V, Å3
Z
C(CH2)4CH2).
105.837(1)
Rea ction of 9 w ith Tr ieth yla m in e. A solution of 9 (15
mg, 0.018 mmol) in 0.5 mL of dichloromethane-d2 in an NMR
tube was treated with triethylamine (2.5 µL, 0.018 mmol). The
NMR tube was sealed under argon, and after 10 min measure-
ments were made. Complex 1 was obtained.
Rea ction of 10 w ith Tr ieth yla m in e. A solution of 10 (15
mg, 0.018 mmol) in 0.5 mL of dichloromethane-d2 in an NMR
tube was treated with triethylamine (2.5 µL, 0.018 mmol). The
NMR tube was sealed under argon, and after 10 min measure-
ments were made. Complex 2 was obtained.
P r ep a r a tion of OsCl2(dCdCHP h )(P iP r 3)2 (11). Method
A: A solution of 1 (100 mg, 0.135 mmol) in toluene was heated
to reflux during 24 h. The resulting purple solution was
evaporated to dryness, and addition of methanol yielded a
purple solid that was washed with methanol (2 × 2 mL) and
dried in vacuo. Yield: 55 mg (60%). Method B: As described
for method A starting from 100 mg (0.128 mmol) of 2. Yield:
50 mg (57%). Anal. Calcd for C26H48Cl2OsP2: C, 45.67; H, 7.08.
Found: C, 45.50; H, 7.26. IR (KBr, cm-1): ν(OsdCdC) 1611
(s). 1H NMR (C6D6, 20 °C): δ 7.10 (t, J H-H ) 7.5, 2H, Hmeta-Ph);
6.72 (d, J H-H ) 7.5, 2H, Hortho-Ph); 6.66 (t, J H-H ) 7.5, 1H,
1617.8(2)
2
1.446
D
calc, g cm-3
1.480
Data Collection and Refinement
Bruker-Siemens CCD
0.71073
diffractometer
λ(Mo KR), Å
monochromator
F, mm-1
graphite oriented
4.14
4.13
scan type
2θ range, deg
temp, K
no. of data
collect
ω scans at different n values
5 e 2θ e 52
293.0(2)
4640
5 e 2θ e 50
173.0(2)
8996
(h: -10, 11; k: -12, 14; (h: -11, 11; k: -11, 12;
l: -16, 6)
2406 (merging R
factor 0.0261)
184
l: -18, 19)
5667 (merging R
factor 0.0481)
318
no. of unique
data
no. of params
refined
a
R1 [F2 > 2σ(F2)] 0.0282
0.0456
0.1113
0.897
b
wR2 [all data] 0.0714
Sc [all data]
1.009
R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) {∑[w(Fo - Fc2)2]/
a
b
2
H
para-Ph); 3.04 (m, 6H, PCH); 2.14 (t, J H-P ) 2.7, 1H, OsdCd
CHPh); 1.34 (dvt, J H-H ) 7.2, N ) 13.5, 36H, PCHCH3). 13C-
{1H} NMR plus DEPT (C6D6, 20 °C): δ 278.9 (t, J C-P ) 9.6,
OsdC); 131.1 (t, J C-P ) 2.0, Cipso-Ph); 127.8, 125.1, and 123.7
(all s, CPh); 110.0 (t, J C-P ) 4.0, OsdCdC); 23.7 (vt, N ) 23.3,
PCH); 19.6 (s, PCHCH3). 31P{1H} NMR (C6D6, 20 °C): δ 5.5
(s). MS (FAB+): m/z 684 (M+ - Cl).
∑[w(Fo2)2]}1/2. Goof ) S ) {∑[w(Fo - Fc2)2]/(n - p)}1/2, where n
is the number of reflections, and p is the number of refined
parameters.
c
2
Complex 3 was solved and refined in both P21 and P21/m
space groups, according to the observed value of Z ) 2 and
systematic absences. However, a careful check of the refined
geometry revealed the P21/m space group as more appropriate.
The -CHdCH2 group of the allylamine ligand of 5 was
found to be disordered. This disorder was modeled with two
moieties (C(13a), C(14a) and C(13b), C(14b)) and refined with
complementary occupancy factors (0.53(3) a, and 0.47(3) b) as
isotropic atoms.
Complex 5 crystallizes with two molecules of toluene with
occupancy 0.5, which were refined with restrained geometry.
The vinylidene (H01), imine (H02), and amine (H(03) and
H(04)) hydrogen atoms of complex 5 were refined as free
isotropic atoms, with the same bond distance to the N(2)
nitrogen atom for H(03) and H(04).
Cr ysta l Da ta for OsCl(dNdCMe2)(dCdCHP h )(P iP r 3)2
(3) an d OsCl2(dCdCHP h )(NHdC(Me)2}(NH2CH2CHdCH2)-
(P iP r 3) (5). A summary of the fundamental crystal and
refinement data of the compounds 3 and 5 is given in Table 3.
Crystals of 3 and 5 were mounted on a Bruker Smart CCD(3)
and Bruker Smart APEX CCD diffractometers equipped with
a normal focus, 2.4 kW sealed tube X-ray source (molybdenum
radiation, λ ) 0.71073 Å) operating at 50 kV and 30 mA. Data
were collected over a hemisphere by a combination of three
sets. The cell parameters were determined and refined by
least-squares fit of all collected reflections. Each frame expo-
sure time was 20 s (3) or 10 s (5) covering 0.3° in ω. Coverage
of the unique sets was over 100% complete to al least 25° in
θ. The first 50 (3) or 100 (5) frames were collected at the end
of the data collection to monitor crystal decay. The absorption
correction was made using SADABS.35 The structure was
solved by Multan and Fourier methods using SHELXS.36 Full-
matrix least-squares refinement was carried out using
Ackn owledgm en t. Financial support from the DGES
of Spain (Project PB98-1591) is acknowledged. R.C.
thanks the “Ministerio de Ciencia y Tecnolog´ıa” for a
grant.
SHELXL9735 minimizing w(Fo2 - Fc )2. Weighted R factors (Rw)
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates and equivalent isotropic displacement coefficients,
anisotropic thermal parameters, experimental details of the
X-ray studies, and bond distances and angles for 3 and 5. This
material is available free of charge via the Internet at
http://pubs.acs.org.
2
and goodness of fit S are based on F2; conventional R factors
are based on F.
(35) SADABS, Smart Apex v. 5; Bruker Analytical X-ray Systems:
Madison, WI.
(36) Sheldrick, G. M. SHELXS; University of Go¨ttingen: Go¨ttingen,
Germany, 1997.
OM001044J