Formation of imine-vinylidene-osmium(II) derivatives by hydrogen transfer from alkenyl ligands to azavinylidene groups in alkenyl-azavinylidene-osmium(IV) complexes

Article abstract of DOI:10.1021/om0005295

Treatment at room temperature of the hydride-azavinylidene complexes OsHCl₂(=N=CR₂)(PⁱPr₃)₂ [CR₂ = CMe₂ (1), C(CH₂)₄CH₂ (2)] with Ag[CF₃

Full text of DOI:10.1021/om0005295

5454
Organometallics 2000, 19, 5454-5463
F or m a tion of Im in e-Vin ylid en e-Osm iu m (II) Der iva tives
by Hyd r ogen Tr a n sfer fr om Alk en yl Liga n d s to
Aza vin ylid en e Gr ou p s in
Alk en yl-Aza vin ylid en e-Osm iu m (IV) Com p lexes
Ricardo Castarlenas, Miguel A. Esteruelas,* and Enrique On˜ate
Departamento de Quı´mica Ino´rganica-Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received J une 21, 2000
Treatment at room temperature of the hydride-azavinylidene complexes OsHCl2(dNdCR2)-
(PiPr3)2 [CR2 ) CMe2 (1), C(CH2)4CH2 (2)] with Ag[CF3SO3] and the subsequent addition at
-25 °C of phenylacetylene to the resulting solutions affords the alkenyl-azavinylidene
derivatives [Os{(E)-CHdCHPh}Cl(dNdCR2)(PiPr3)2][CF3SO3] [CR2 ) CMe2 (3), C(CH2)4CH2
(4)], where the Hâ atoms of the alkenyl ligands interact with the osmium atoms to form
agostic bonds. The addition at -30 °C of NaCl to tetrahydrofuran solutions of 3 and 4
produces the split of the agostic interactions and the formation of the neutral six-coordinate
alkenyl-azavinylidene compounds Os{(E)-CHdCHPh}Cl2(dNdCR2)(PiPr3)2 [CR2 ) CMe2
(5), C(CH2)4CH2 (6)]. In dichloromethane at room temperature complexes 5 and 6 evolve
into the imine-vinylidene derivatives OsCl2(dCdCHPh)(NHdCR2)(PiPr3)2 [CR2 ) CMe2 (7),
C(CH2)4CH2) (8)], as a result of the hydrogen transfer from the styryl ligands to the
azavinylidene groups. The structure of 7 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
octahedron with the imine group disposed trans to a chlorine atom and cis to the other one.
The N-H hydrogen atom of the imine interacts with the latter to form an intramolecular
N-H‚‚‚Cl hydrogen bond, which is manifested by a short Cl‚‚‚‚H separation of 2.366 Å and
a Cl-Os-N angle of 77.34(18)°, largely deviated from the ideal value of 90°. Complexes 3
and 4 also react with water at -20 °C to give the cationic imine-vinylidene derivatives
[OsCl(dCdCHPh)(NHdCR2)(H2O)(PiPr3)2][CF3SO3] [CR2 ) CMe2 (9), C(CH2)4CH2 (10)]. The
structure of 9 in the solid state has been also determined by an X-ray diffraction study. The
geometry around the metal center is octahedral with the imine group disposed trans to
chlorine atom and cis to the water molecule. In this case the N-H hydrogen atom of the
imine interacts with the oxygen atom of water molecule. The N-H‚‚‚O hydrogen bond is
manifested by an O‚‚‚H separation of 2.36 Å and a N-Os-O angle of 78.3(2)°. The formation
of 9 and 10 proceeds via the cationic six-coordinate alkenyl-azavinylidene-osmium(IV)
intermediates [Os{(E)-CHdCHPh}Cl(dNdCR2)(H2O)(PiPr3)2][CF3SO3] [CR2 ) CMe2 (11), C-
1
(CH2)4CH2 (12)], which have been characterized in solution at -90 °C by H and 31P{1H}
NMR spectroscopy. Complexes 3 and 4 react with acetonitrile to give [OsCl(dCdCHPh)-
(NHdCR2)(CH3CN)(PiPr3)2][CF3SO3] [CR2 ) CMe2 (13), C(CH2)4CH2 (14)] via the intermedi-
ates [Os{(E)-CHdCHPh}Cl(dNdCR2)(CH3CN)(PiPr3)2[CF3SO3] [CR2 ) CMe2 (15), C-
(CH2)4CH2 (16)].
In tr od u ction
forward route arises from the activation of terminal
alkynes which, depending upon of the nucleophilicity
of the metallic center, initially give η2-coordinated
alkyne or alternatively hydride-alkynyl intermediates.
The η2-alkynes evolve by direct 1,2-hydrogen migration
over the carbon-carbon triple bond. The hydride-
alkynyl intermediates dissociate the hydride as a proton
to yield alkynyl species; subsequently, the protonation
Vinylidene complexes are considered the central point
of important selective transformations of terminal
alkynes with atom economy.1 Several methods have
been employed for their preparation.2 The most straight-
(1) Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res. 1999, 32, 311.
(2) Bruce, M. I. Chem. Rev. 1991, 91, 197.
10.1021/om0005295 CCC: $19.00 © 2000 American Chemical Society
Publication on Web 11/15/2000

Imine-Vinylidene-Osmium(II) Derivatives
Organometallics, Vol. 19, No. 25, 2000 5455
of the alkynyl group at the Câ atom affords the vi-
nylidene derivatives.3 In agreement with the last, the
electrophilic addition to alkynyl complexes has shown
to be also a general strategy to prepare vinylidene
complexes.2 In addition, the deoxygenation of acylmetal
derivatives by treatment with (CF3SO2)2O,4 the depro-
tonation of metal carbynes,5 the rearrangement of
alkylidene metallacyclobutane species,6 and the reduc-
tion of allenylidene compounds should be mentioned.7
With some exceptions,8 from hydride complexes, the
most favored pathway is the insertion of the triple bond
of terminal alkynes into the M-H bonds to form alkenyl
intermediates, which undergo R-hydrogen elimination.9
The dehydrochlorination of chloroalkenyl compounds
has been also used.2,10
nucleophilic attack, to form functionalized amines.13 In
particular, complexes containing N-protio imines with
low molecular weight have proven difficult to isolate.
The reaction of Cr(CO)5{dC(OMe)Me} with oximes of
aliphatic, alicyclic, and aromatic ketones affords Cr-
(CO)5(NHdCRR′), including dimethyl imine.14 Related
compounds of chromium, molybdenum, tungsten, and
iron have been prepared from the corresponding metal-
ammonia starting materials and ketones.15 The benzo-
phenone imine derivatives M(CO)5(NHdCPh2) (M ) Cr,
W) have been synthesized by reaction of M(CO)5(dCPh2)
with trimethylsilyl azide.16 Gladysz and co-workers have
reported imine complexes of the type [Re(η5-C5H5)(NO)-
(NHdCRR′)(PPh3)][CF3SO3], which are obtained by
displacement of triflate by the free imine or by addition
of nucleophiles to cationic nitrile complexes followed by
protonation.17 Complexes Os(C2Ph)2(CO)(NHdCPh2)-
(PiPr3)218 and MHCl(CO)(NHdCPh2)(PiPr3)2 (M ) Ru,19a
Os19b) have been obtained by addition of benzophenone
imine to the corresponding five-coordinate precursors.
Imine complexes are intermediate states during the
transformations between amine and nitrile deriva-
tives.11 However, there are comparatively few examples
of monodentate nitrogen-bonded imine compounds, as
a consequence of the weak Lewis basicity of the imine
nitrogen atom,12 and the vulnerability of the imines to
The protonation of OsH(CO)(NHdC(Ph)C6H4}(CO)-
(PiPr3)2 with HBF4‚OEt2 gives [OsH(CO)(NHdCPh2)-
(PiPr3)2]BF4, which by reaction with carbon monoxide
or trimethyl phosphite affords [OsH(CO)(NHdCPh2)L-
(PiPr3)2]BF4 [L ) CO, P(OMe)3].20 Half-sandwich ruthe-
nium and osmium complexes containing aldimine and
benzophenone imine ligands have been also synthe-
sized.21
(3) (a) Silvestre, J .; Hoffmann, R. Helv. Chem. Acta 1985, 68, 1461.
(b) Wakatsuki, Y.; Koga, N.; Yamazaki, H.; Morokuma, K. J . Am.
Chem. Soc. 1994, 116, 8105. (c) de los Rios, I.; J ime´nez-Tenorio, M.;
Puerta, M. C.; Valerga, P. J . Chem. Soc., Chem. Commun. 1995, 1757.
(d) Wakatsuki, Y.; Koga, N.; Werner, H.; Morokuma, K. J . Am. Chem.
Soc. 1997, 119, 360. (e) de los Rios, I.; J ime´nez-Tenorio, M.; Puerta,
M. C.; Valerga, P. J . Am. Chem. Soc. 1997, 119, 6529. (f) Bustelo, E.;
J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga, P. Organometallics 1999,
18, 950. (g) Bustelo, E.; J ime´nez-Tenorio, M.; Puerta, M. C.; Valerga,
P. Organometallics 1999, 18, 4563. (h) Puerta, M. C.; Valerga, P. Coord.
Chem. Rev. 1999, 193-195, 977. (i) Baya, M.; Crochet, P.; Esteruelas,
M. A.; Gutie´rrez-Puebla, E.; Lo´pez, A. M.; Modrego, J .; On˜ate, E.; Vela,
N. Organometallics 2000, 19, 2585.
We have recently 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)-
(4) (a) Boland-Lussier, B. E.; Churchill, M. R.; Hughes, R. P.;
Rheingold, A. L. Organometallics 1982, 1, 628. (b) Bly, R. S.; Raja,
M.; Bly, R. K. Organometallics 1992, 11, 1220.
(PiPr3)2 [CR2 ) CMe2, C(CH2)4CH2],22 which afford the
corresponding hydride-azavinylidene-osmium(IV) com-
plexes OsHCl2(dNdCR2)(PiPr3)2 by addition of HCl.23
As a part of our work on the reactivity of transition
(5) (a) Baker, P. K.; Barber, G. K.; Green, M.; Welch, A. J . J . Am.
Chem. Soc. 1980, 102, 7811. (b) Gill, D. S.; Green, M. J . Chem Soc.,
Chem. Commun. 1981, 1037. (c) Bourgault, M.; Castillo, A.; Esteruelas
M. A.; On˜ate, E.; Ruiz, N. Organometallics 1997, 16, 636. (e) Esteru-
elas, M. A.; Oliva´n, M.; On˜ate, E.; Ruiz, N.; Tajada, M. A. Organome-
tallics 1999, 18, 2953. (e) Buil, M. L.; Eisenstein, O.; Esteruelas, M.
A.; Garc´ıa-Yebra, C.; Gutie´rrez-Puebla, E.; Oliva´n, M.; On˜ate, E.; Ruiz,
N.; Tajada M. A. Organometallics 1999, 18, 8, 4949. (f) Buil, M. L.;
Esteruelas, M. A.; Garc´ıa-Yebra, C.; Gutie´rrez-Puebla, E.; Oliva´n, M.
Organometallics 2000, 19, 2184.
(6) Buchwald, S. L.; Grubbs, R. H. J . Am. Chem. Soc. 1983, 105,
5490.
(7) Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa, J .
I. Organometallics 1998, 17, 3479.
(8) (a) Esteruelas, M. A.; Oro L. A.; Valero, C. Organometallics 1995,
14, 3596. (b) Crochet P.; Esteruelas, M. A.; Lo´pez, A. M.; Mart´ınez,
M.-P.; Oliva´n, M.; On˜ate, E.; Ruiz, N. Organometallics 1998, 17, 4500.
(9) (a) van Asselt, A.; Burger, B. J .; Gibson, V. C.; Bercaw, J . E. J .
Am. Chem. Soc. 1986, 108, 5347. (b) Dziallas, M.; Werner, H. J .
Organomet. Chem. 1987, 333, C29. (c) Beckhaus, R.; Thiele, K.-H.;
Stro¨hl, D. J . Organomet. Chem. 1989, 369, 43. (d) Bell, T. W.;
Haddleton, D. M.; McCamley, A.; Partridge, M. G.; Perutz, R. N.;
Willner, H. J . Am. Chem. Soc. 1990, 112, 9212. (e) Gibson, V. C.;
Parkin, G.; Bercaw, J . E. Organometallics 1991, 10, 220. (f) Beckhaus,
R. J . Chem. Soc., Dalton Trans. 1997, 1991. (g) Luinstra, G. A.; Teuben,
J . H. Organometallics 1992, 11, 1793. (h) Beckhaus, R. Angew. Chem.,
Int. Ed. Engl. 1997, 36, 686. (i) Alvarado, Y.; Boutry, O.; Gutie´rrez,
E.; Monge, A.; Nicasio, M. C.; Poveda, M. L.; Pe´rez, P. J .; Ru´ız, C.;
Bianchini, C.; Carmona E. Chem. Eur. J . 1997, 3, 860. (j) Oliva´n, M.;
Clot, E.; Eisenstein, O.; Caulton, K. G. Organometallics 1998, 17, 3091.
(10) Weinand, R.; Werner, H. J . Chem. Soc., Chem. Commun. 1985,
1145.
(11) (a) Ridd, M. J .; Keene, F. R. J . Am. Chem. Soc. 1981, 103, 5733.
(b) Adcock, P. A.; Keene, F. R. J . Am. Chem. Soc. 1981, 103, 6494. (c)
Feng, S. G.; Templeton, J . L. J . Am. Chem. Soc. 1989, 111, 6477. (d)
Feng, S. G.; Templeton, J . L. Organometallics 1992, 11, 1295. (e) Yeh,
W.-Y.; Ting, C.-S.; Peng, S.-M.; Lee, G.-H. Organometallics 1995, 14,
1417. (f) Gunnoe, T: B.; White, P. S.; Templeton, J . L. J . Am. Chem.
Soc. 1996, 118, 6916. (g) Francisco, L. W.; White, P. S.; Templeton, J .
L. Organometallics 1996, 15, 5127.
(13) (a) Hoberg, H.; Go¨tz, V.; Kru¨ger, C.; Tsay, Y. H.J . Organomet.
Chem. 1979, 169, 209. (b) Buchwald, S. L.; Watson, B. T.; Wannama-
ker, M. W.; Dewan, J . C. J . Am. Chem. Soc. 1989, 111, 4486. (c) Durfee,
L. D.; Hill, J . E.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1990,
9, 75. (d) Martin, G. C.; Boncella, J . M.; Wucherer, E. J . Organome-
tallics 1991, 10, 2804. (e) Faller, J . W.; Ma, Y.; Smart, C. J .; Diverdi,
M. J . J . Organomet. Chem. 1991, 420, 237. (f) Richter-Addo, G. B.;
Knight, D. A.; Dewey, M. A.; Arif, A. M.; Gladysz, J . A. J . Am. Chem.
Soc. 1993, 115, 11863. (g) Cantrell, W. R., J r.; Richter-Addo, G. B.;
Gladysz, J . A. J . Organomet. Chem. 1994, 472, 195.
(14) Fischer, E. O.; Knauss, L. Chem. Ber. 1970, 103, 1262.
(15) Sellmann, D.; Thallmair, E. J . Organomet. Chem. 1979, 164,
337.
(16) Fischer, H.; Zeuner, S. J . Organomet. Chem. 1985, 286, 201.
(17) (a) Knight, D. A.; Dewey, M. A.; Stark, G. A.; Bennett, B. K.;
Arif, A. M.; Gladysz, J . A. Organometallics 1993, 12, 4523. (b) Stark,
G. A.; Gladysz, J . A. Inorg. Chem. 1996, 35, 5509.
(18) Esteruelas, M. A.; Lahoz, F. J .; Lo´pez, A. M.; On˜ate, E.; Oro,
L. A. Organometallics 1995, 14, 2496.
(19) (a) Bohanna, C.; Esteruelas, M. A.; Lo´pez A. M.; Oro L. A. J .
Organomet. Chem. 1996, 526, 73. (b) Daniel, T.; Werner, H. Z.
Naturforsch. B 1992, 47, 1707.
(20) Albe´niz, M. J .; Buil, M. L.; Esteruelas, M. A.; Lo´pez, A. M. J .
Organomet. Chem. 1997, 545-546, 495.
(21) (a) Faller, J . W.; Ma, Y.; Smart, C. J .; Diverdi, M. J . J .
Organomet. Chem. 1991, 420, 273. (b) Daniel, T.; Mu¨ller, M.; Werner,
H. Inorg. Chem. 1991, 30, 3120. (c) Daniel, T.; Knaup, W.; Dziallas,
M.; Werner, H. Chem. Ber. 1993, 126, 1981. (d) Werner, H.; Daniel,
T.; Knaup, W.; Nu¨rnberg, O. J . Organomet. Chem. 1993, 462, 309. (e)
Werner, H.; Daniel, T.; Braun, T.; Nu¨rnberg, O. J . Organomet. Chem.
1994, 480, 145.
(22) Castarlenas, R.; Esteruelas, M. A.; Gutie´rrez-Puebla, E.; J ean,
Y.; Lledo´s, A.; Mart´ın, M.; Toma`s, J . Organometallics 1999, 18, 4296.
(23) Castarlenas, R.; Esteruelas, M. A.; Gutie´rrez-Puebla, E.; J ean,
Y.; Lledo´s, A.; Mart´ın, M.; On˜ate, E,; Toma`s, J . Organometallics 2000,
19, 3100.
(12) Mehrota, R. C. In Comprehensive Coordination Chemistry;
Wilkinson, G.; Gillard, R. D., McCleverty, J . A., Eds.; Pergamon:
Oxford, England, 1987; Vol 2, pp 269-287.

5456 Organometallics, Vol. 19, No. 25, 2000
Castarlenas et al.
Sch em e 1
between 2 and 4 ppm to higher field in comparison with
those found in styryl complexes without agostic interac-
tion. The value of the Hâ-P coupling constant in 3 (the
Hâ resonance of 4 appears as a broad signal) of 10.2 Hz
is also unusual and higher than that observed in styryl
compounds without agostic interaction (about 2 Hz).26
In contrast, the values of the HR-Hâ coupling constants
(11.7 Hz for 3 and 10.8 Hz for 4) are lower than that
expected for an E arrangement of the alkenyl groups
(between 16 and 18 Hz),26 but compare well with that
found in the complex OsH{C6H4-2-(E-CHdCHPh)}(CO)-
(PiPr3)2 (13.6 Hz),27 where the E stereochemistry at the
carbon-carbon double bond and the agostic Os-Hâ
interaction have been proven by X-ray diffraction analy-
sis. Despite the low values of the HR-Hâ coupling
constant, the E stereochemistry at the carbon-carbon
double bond of the styryl groups of 3 and 4 is a fact.
The saturation of the HR resonance of 3 increases the
intensity of the ortho-H resonance of the phenyl group
(23%), while the Hâ resonance does not show any NOE
effect. In the 13C{1H} NMR spectra at -40 °C, the CR
atoms of the styryl ligands give rise to triplets at 144.0
(3) and 143.6 (4) with C-P coupling constants of 6 and
5 Hz, respectively, whereas the Câ atoms display broad
signals at 137.5 ppm in both cases. The resonances
corresponding to the CdN carbon atoms of the azavi-
nylidene ligands appear at 160.6 (3) and 161.9 (4) as
broad signals. The 31P{1H} NMR spectra show singlets
at 0.1 (3) and 2.1 (4) ppm, in agreement with the
mutually trans disposition of the phosphine ligands.
Complexes 3 and 4, which were isolated as green
solids in high yield (about 70%), are stable for one month
if kept as solids under argon at -20 °C. In solution of
dichloromethane they are stable for a few hours at
temperatures lower than 0 °C. At room temperature
they evolve into mixtures of five products, according to
the 31P{1H} NMR spectra of the mixtures. The addition
at -30 °C of 3.6 equiv of NaCl to tetrahydrofuran
solutions of 3 and 4 leads to the neutral alkenyl-
azavinylidene derivatives Os{(E)-CHdCHPh}Cl2(dNdC
metal hydride complexes toward terminal alkynes,24 we
have now investigated the reactions of the above-
mentioned hydride-azavinylidene compounds with phen-
ylacetylene. In this paper, we report the discovery of a
novel reaction, the hydrogen transfer from a styryl
ligand to azavinylidene groups, which affords complexes
containing both functional groups vinylidene and imine.
Resu lts a n d Discu ssion
F or m a t ion a n d Ch a r a ct er iza t ion of Neu t r a l
Imine-Vinylidene Complexes.ComplexesOsHCl2(dNd
CR2)(PiPr3)2 [CR2 ) CMe2 (1), C(CH2)4CH2 (2)] do not
react with phenylacetylene due to their saturated
character. However, the treatment at room temperature
of dichloromethane solutions of 1 and 2 with 1.0 equiv
of Ag[CF3SO3] and the subsequent addition at -25 °C
of 1.2 equiv of phenylacetylene affords, after 5 h, the
alkenyl-azavinylidene complexes [Os{(E)-CHdCHPh}-
R2)(PiPr3)2 [CR2 ) CMe2 (5), C(CH2)4CH2 (6)], as ex-
pected from the lability of the agostic interactions.
Complexes 5 and 6, which were isolated as orange solids
in about 80% yield, are the result of the kinetically
disfavored insertion of phenylacetylene into the Os-H
bonds of 1 and 2.
Cl(dNdCR2)(PiPr3)2][CF3SO3] [CR2 ) CMe2 (3), C(C-
H2)4CH2 (4)], as a result of the extraction of a chlorine
ligand from 1 and 2 and the insertion of the carbon-
carbon triple bond of the alkyne into the Os-H bonds
of the resulting unsaturated intermediates (Scheme 1).
The unsaturated character of 3 and 4 is strongly
supported by the IR spectra of these compounds in KBr,
which contain the characteristic stretching bands of the
free [CF3SO3] anion25 at about 1270, 1230, 1160, and
In the IR spectra of 5 and 6, the most noticeable
feature is the absence of any band due to the [CF3SO3]-
anion. The 1H NMR spectra reflect the split of the
agostic interactions as a consequence of the coordination
of chlorine to 3 and 4. Thus, the vinyl resonances of the
styryl ligands are observed at about 12 and 5 ppm, as
doublets with HR-Hâ coupling constants of about 17 Hz.
The spectra also reflect the mutually cis disposition of
the chlorine ligands, showing two iPr-methyl chemical
shifts as a result of the prochirality of the phosphorus
atom of the phosphines. In the 13C{1H} NMR spectra,
the CR atoms of the styryl ligands give rise to triplets
at 133.4 (5) and 138.9 (6) ppm, with C-P coupling
constants of 3.5 and 2.8 Hz, respectively, whereas the
resonances corresponding to the Câ atoms are observed
as singlets at 139.4 (5) and 137.5 (6) ppm. The CdN
1
1030 cm-1. The H NMR spectra at room temperature
confirm the presence of the styryl groups with an E
stereochemistry and suggest that the Hâ atoms of the
alkenyl ligands interact with the osmium atoms of 3 and
4 to form agostic bonds. Thus, the resonances corre-
sponding to the vinylic HR atoms appear at 7.81 (3) and
7.84 (4) ppm, in agreement with the chemical shifts
observed in other osmium- and ruthenium-styryl
complexes.26 However, the resonances due to the vinylic
Hâ atoms are observed at 3.92 (3 and 4) ppm, shifted
(24) Buil, M. L.; Elipe, S.; Esteruelas, M. A.; On˜ate, E.; Peinado,
E.; Organometallics 1997, 16, 5748, and references therein.
(25) Lawrence, G. A. Chem. Rev. 1986, 86, 17.
(26) Werner, H.; Esteruelas, M. A.; Otto, H. Organometallics 1986,
5, 2295.
(27) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Sola, E.
J . Am. Chem. Soc. 1996, 118, 89.

Imine-Vinylidene-Osmium(II) Derivatives
Organometallics, Vol. 19, No. 25, 2000 5457
phosphorus atoms of the triisopropylphosphine in trans
position [P(1)-Os-P(2) ) 174.99(8)°]. The perpendicu-
lar plane is formed by the chlorine ligands mutually cis
disposed [Cl(1)-Os-Cl(2) ) 89.50(7)°], the C(4) atom
of the vinylidene trans disposed to Cl(2) [Cl(2)-Os-C(4)
) 170.9(2)°], and the nitrogen atom of the imine group
trans disposed to Cl(1) [Cl(1)-Os-N ) 166.03(16)°].
The vinylidene ligand is bound to the metal in a
nearly linear fashion with an Os-C(4)-C(5) angle of
173.7(6)°. The Os-C(4) [1.820(6) Å] and C(4)-C(5)
[1.322(9) Å] bond lengths compare well with those found
in other osmium-vinylidene28 complexes and support
the vinylidene formulation.
The imine ligand is bound to the metal in a bent
fashion, with a Os-N-C(1) angle of 142.5(6)°, which
compares well with the Re-N-C angle found in the
complex [Re(η5-C5H5)(NO)(NHdCPh2)(PPh3)]+ [136.2-
(3)°].17a The Os-N distance [2.072(7) Å] is between 0.2
and 0.3 Å longer than those reported in the related
azavinylidene complexes OsHCl2{dNdC(CH2)4CH2}-
(PiPr3)2 [1.789(12) and 1.777(12) Å] and OsCl3{dNdC-
F igu r e 1. Molecular diagram for OsCl2(dCdCHPh)(NHd
CMe2)(PiPr3)2 (7). Thermal ellipsoids are shown at 50%
probability.
(CH2)4CH2}(PiPr3)2 [1.808(10) and 1.806(10) Å]23 and
supports the Os-N single bond formulation. The N-C(1)
bond length [1.270(9) Å] is similar to those observed in
other imine transition metal complexes (about 1.27
Å),17a,29 azavinylidene compounds (between 1.27 and
1.30 Å),23 organic azaallenium cations (between 1.23 and
1.33 Å),30 and the 2-azaallenyl complexes Cr{C(OEt)d
NdCtBu2}(CO)5 [1.272(5) and 1.264(5) Å],31 Cr{C(Ph)d
NdCHPh}(CO)5 [1.260(4) and 1.265(4) Å],32 and [Ru(η5-
C5H5){C(CHdCPh2)dNdCPh2}(CO)(PiPr3)]+ [1.283(9)
and 1.252(9) Å].33
The imine H(N) hydrogen atom was found in the
difference Fourier maps and refined as an isotropic atom
together with the rest of the non-hydrogen atoms of the
structure, giving a N-H(N) distance of 0.87(7) Å.
Interestingly, the separation between this atom and the
chlorine ligand Cl(2) (2.366 Å) is 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
is an intramolecular Cl‚‚‚H-N hydrogen bond between
these atoms, as a result of the interaction of the
electronegative chlorine atom with the acidic N-H
hydrogen. The Cl‚‚‚H interaction gives rise to a four-
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex
OsCl2(dCdCHP h )(NHdCMe2)(P iP r 3)2 (7)
Os-Cl(1)
Os-Cl(2)
Os-P(1)
Os-P(2)
Os-N
2.4165(19)
2.5669(19)
2.466(2)
2.447(2)
2.072(7)
1.820(6)
N-C(1)
1.270(9)
1.523(11)
1.473(10)
1.322(9)
1.453(10)
0.87(7)
C(1)-C(2)
C(1)-C(3)
C(4)-C(5)
C(5)-C(6)
N-H(01)
Os-C(4)
Cl(1)-Os-Cl(2)
Cl(1)-Os-P(1)
Cl(1)-Os-P(2)
Cl(1)-Os-N
Cl(1)-Os-C(4)
Cl(2)-Os-P(1)
Cl(2)-Os-P(2)
Cl(2)-Os-N
89.50(7)
85.95(7)
89.06(8)
166.03(16)
96.7(2)
92.90(7)
86.60(7)
77.34(18)
170.9(2)
174.99(8)
90.00(18)
P(1)-Os-C(4)
P(2)-Os-N
94.1(2)
94.75(19)
86.9(2)
P(2)-Os-C(4)
N-Os-C(4)
96.9(3)
Os-N-C(1)
142.5(6)
173.7(6)
119.5(7)
124.5(8)
116.0(7)
126.2(7)
Os-C(4)-C(5)
N-C(1)-C(2)
N-C(1)-C(3)
C(2)-C(1)-C(3)
C(4)-C(5)-C(6)
Cl(2)-Os-C(4)
P(1)-Os-P(2)
P(1)-Os-N
carbon atoms of azavinylidene ligands display singlets
at about 151 ppm. The 31P{1H} spectra contain singlets
at -51.4 (5) and -49.6 (6) ppm.
Complexes 5 and 6 are stable for long times if kept
as solids under argon at temperatures lower than -20
°C. In solution of chloroform-d or dichloromethane-d2,
they are also stable for a few hours at temperatures
lower than 0 °C. At room temperature, they slowly
evolve into the imine-vinylidene derivatives OsCl2-
membered Os-Cl‚‚‚H-N ring, which is almost planar
(28) (a) 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.
(29) Kukushkin, V. Y.; Pakhomova, T. B.; Kukushkin, Y. N.;
Herrman, R.; Wagner, G.; Pombeiro, A. J . L. Inorg. Chem. 1998, 37,
6511.
(dCdCHPh)(NHdCR2)(PiPr3)2 [CR2 ) CMe2 (7), C-
(CH2)4CH2 (8)], as a result of the hydrogen transfer from
the styryl ligand to the azavinylide groups (Scheme 1).
Complexes 7 and 8 were isolated as orange solids in
80 and 78% yield, respectively, and characterized by MS,
(30) (a) 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.
(31) Seitz, F.; Fischer, H.; Riede, J . J . Organomet. Chem. 1985, 287,
87.
1
elemental analysis, and IR, H, 13C{1H}, and 31P{1H}
NMR spectroscopy. Complex 7 was further character-
ized by an X-ray crystallographic study. A view of the
molecular geometry of this complex is shown in Figure
1. Selected bond distances and angles are listed in Table
1.
(32) Aumann, R.; Althaus, S.; Kru¨ger, S.; Betz, P. Chem. Ber. 1989,
122, 357.
(33) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
The geometry around the osmium atom can be
rationalized as a distorted octahedron with the two

5458 Organometallics, Vol. 19, No. 25, 2000
Castarlenas et al.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex
[OsCl(dCdCHP h )(NHdCMe2)(H2O)(P iP r 3)2]
[CF 3SO3]‚C4H8O (9)
Os-Cl
2.3959(18)
2.4663(18)
2.4679(19)
2.067(5)
2.281(6)
1.803(7)
N-C(9)
1.290(10)
1.494(11)
1.492(11)
1.344(10)
1.464(10)
Os-P(1)
Os-P(2)
Os-N
C(9)-C(10)
C(9)-C(11)
C(1)-C(2)
C(2)-C(3)
Os-O(4)
Os-C(1)
Cl-Os-P(1)
Cl-Os-P(2)
Cl-Os-O(4)
Cl-Os-N
Cl-Os-C(1)
P(1)-Os-P(2)
P(1)-Os-O(4)
P(1)-Os-N
P(1)-Os-C(1)
P(2)-Os-O(4)
91.68(6)
86.20(6)
81.53(16)
158.55(18)
99.5(2)
177.42(7)
87.36(15)
94.59(17)
87.7(2)
P(2)-Os-N
87.91(17)
91.2(2)
78.3(2)
175.0(3)
101.2(3)
142.7(6)
176.5(6)
120.4(8)
123.1(7)
127.0(7)
P(2)-Os-C(1)
O(4)-Os-N
O(4)-Os-C(1)
N-Os-C(1)
Os-N-C(9)
Os-C(1)-C(2)
N-C(9)-C(10)
N-C(9)-C(11)
C(1)-C(2)-C(3)
93.78(15)
about 114 ppm, also as triplets but with C-P coupling
constants of about 3 Hz. The CdN carbon atoms of the
imine groups display singlets between 177 and 183 ppm.
The 31P{1H} NMR spectra show singlets at -21.7 (7)
and -20.8 (8) ppm.
F or m a tion a n d Ch a r a cter iza tion of Ca tion ic
Im in e-Vin ylid en e Com p lexes. When the reactions
of 1 and 2 with Ag[CF3SO3] and phenylacetylene are
carried out in humid solvents, the cationic imine-
vinylidene complexes [OsCl(dCdCHPh)(NHdCR2)(H2O)
F igu r e 2. Molecular diagram for the cation of [OsCl(d
CdCHPh)(NHdCMe2)(H2O)(PiPr3)2][CF3SO3] (9). Thermal
ellipsoids are shown at 50% probability.
with the plane containing the Os, C(4), N, Cl(1), and
Cl(2) atoms. The dihedral angle between this plane and
that containing the N, C(1), C(3), and C(2) atoms is
14.9°. The Cl‚‚‚H-N hydrogen bond appears to have a
strong influence on the Cl(2)-Os-N angle [77.34(18)°],
which largely deviates from the ideal value of 90°. Of
great importance in biological and organic chemistry,34
the hydrogen bonding is presently attracting consider-
able interest in the chemistry of transition metals.5d,35
(PiPr3)2][CF3SO3] [CR2 ) CMe2 (9), C(CH2)4CH2 (10)],
containing a coordinated water molecule, are formed.
These compounds are obtained as red solids in about
70% yield, by addition at -20 °C of 1 equiv of water to
tetrahydrofuran solutions of 3 and 4 (eq 1).
In agreement with the presence of imine ligands in 7
and 8, the IR spectra of these compounds in KBr contain
1
ν(N-H) bands at 3216 (7) and 3202 (8) cm-1. In the H
NMR spectra, the N-H resonances appear at about 11
ppm. These spectra, as those of 5 and 6, are in
accordance with the mutually cis disposition of the
i
chlorine ligands, showing two Pr-methyl chemical
shifts. In addition, they contain triplets with H-P
coupling constants of about 2 Hz, between 1 and 2 ppm,
which correspond to the dCH hydrogen atoms of the
vinylidene ligands. In the 13C{1H} NMR spectra, the
resonances due to the CR carbon atoms of the vinylidene
ligands are observed at about 295 ppm as triplets with
C-P coupling constants of 10.0 (7) and 8.3 (8) Hz,
whereas those corresponding to the Câ atoms appear at
(34) J effrey, G. A.; Saenger, W. Hydrogen Bonding in Biological
Structures; Springer: Berlin, 1991.
(35) (a) 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.; Gutie´rrez-Puebla, E.; Lo´pez, A. M.; On˜ate, E.; Tolosa, J . I.
Organometallics 2000, 19, 275.
Figure 2 shows a view of the molecular geometry of
9. Selected bond distances and angles are listed in Table
2. The geometry around the osmium atom can be
described as a distorted octahedron with the two
phosphorus atoms of the phosphine ligands in trans
position [P(1)-Os-P(2) ) 177.42(7)°]. The chlorine,
vinylidene, imine, and water ligands form the perpen-
dicular plane. The imine is disposed trans to the
chlorine and cis to the water molecule. The angles Cl-
Os-N [158.55(18)°] and N-Os-O(4) [78.3(2)°] largely
deviate from the ideal values of 180° and 90°, respec-
tively, suggesting that in this case there is an intramo-
lecular O‚‚‚H-N hydrogen bond between the water

Imine-Vinylidene-Osmium(II) Derivatives
Organometallics, Vol. 19, No. 25, 2000 5459
Ta ble 3. Cr ysta l Da ta a n d Da ta Collection a n d Refin em en t for OsCl2(dCdCHP h )(NHdCMe2)(P iP r 3)2 (7) a n d
[OsCl(dCdCHP h )(NHdCMe2)(H2O)(P iP r 3)2][CF 3SO3]‚C4H8O (9)
7
9
formula
mol wt
color, habit
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
C
29H55Cl2NOsP2
C30H57ClF3NO4OsP2S × C4H8O
740.78
944.52
orange, prismatic
triclinic, P1h
9.065(3)
11.840(4)
16.591(6)
84.93(2)
85.69(2)
69.77(3)
1662.4(10)
2
red, prismatic
triclinic, P1h
10.788(1)
12.853(2)
15.889(2)
92.554(10)
92.073(14)
109.733(8)
2068.6(4)
42
1.516
Z
D
calc, g cm-3
1.480
Data Collection and Refinement
diffractometer
STOE AED-2
λ(Mo KR), Å
monochromator
µ, mm-1
Brucker-Siemens
Bruker Siemens-P4
3.33
0.71073
graphite oriented
4.11
scan type
ω/2θ
2θ range, deg
temp, K
5° e 2θ e 50°
298.0(2)
5° e 2θ e 50°
173.0(2)
no.of data collect
8044
7851
(h: -10, 3; k: -14, 13; l: -19, 19)
5845 (merging R factor 0.0724)
(h: -12, 1; k: -14, 15; l: -18, 18)
6226 (merging R factor 0.0323)
no. of unique data
no. of params refined
336
525
R1 [F2 > 2σ(F2)]
0.0462
0.0886
1.010
0.0426
0.1077
1.033
a
b
wR2 [all data]
Sc [all data]
R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) {∑[w(Fo - Fc2)2/∑[w|Fo2)2]}1/2
.
c Goof ) S ) {σ[w(Fo - Fc2)2]/(n - p)}1/2, where n is the
a
b
2
2
number of reflections, and p is the number of refined parameters.
molecule and the N-H hydrogen atom of the imine. In
agreement with this, the separation between the atoms
involved in the hydrogen bond (about 2.36 Å) is shorter
than the sum of the van der Waals radii of hydrogen
and oxygen [rvdw(O) ) 1.40 Å]. The O‚‚‚H interaction
-30 °C, the resonances corresponding to the CR atoms
of the vinylidene ligands appear at about 299 ppm as
triplets with C-P coupling constants at about 11 Hz,
whereas the resonances due to the Câ atoms are
observed at about 112 ppm as singlets. The CdN carbon
atoms of the imine groups give rise to singlets between
190 and 185 ppm. The 31P{1H} NMR spectra contain
singlets at -15.3 (9) and -15.0 (10) ppm.
The formation of 9 and 10 involves the initial coor-
dination of water to the metallic centers of 3 and 4 to
give the alkenyl-azavinylidene intermediates [Os{(E)-
CHdCHPh}Cl(dNdCR2)(H2O)(PiPr3)2][CF3SO3] (CR2 )
gives rise to a four-membered Os-O‚‚‚H-N ring, which
is almost planar with the plane containing the Os, Cl,
O(4), N, and C(1) atoms. The dihedral angle between
this plane and that containing the N, C(9), C(10), and
C(11) atoms is 9.4°.36
The vinylidene ligand is bound to the metal in a
nearly linear fashion with an Os-C(1)-C(2) angle of
176.5(6)°, while the imine is bound to the metal in a
bent fashion with an Os-N-C(9) angle of 142.7(6)°. The
Os-C(1) [1.803(7) Å], C(1)-C(2) [1.344(10) Å], Os-N
[2.067(5) Å], and N-C(9) [1.290(10) Å] distances are
similar to the related parameters previously mentioned
for 7.
Complexes 9 and 10 are stable for long times if kept
as solids under argon at -20 °C. In solution of dichlo-
romethane they are stable at temperatures lower than
-20 °C. At room temperature, they rapidly evolve to
give ill-defined straw-colored solids.
In the 1H NMR spectra of 9 and 10 in dichlo-
romethane-d2 at -60 °C, the most noticeable features
are three broad resonances at about 10.5, 5.5, and 2.4
ppm corresponding to the N-H, OH2, and CdCHPh
protons, respectively. In the 13C{1H} NMR spectra at
CMe2 (11), C(CH2)4CH2 (12)], which at -30 °C afford 9
and 10 before the transformations of 3 and 4 into 11
and 12 are complete. These intermediates were char-
acterized in solution at -90 °C by 1H and 31P{1H} NMR
spectroscopy. In the 1H NMR spectra in dichloromethane-
d2, the most noticeable resonances are two doublets at
about 11 and 5 ppm, with H-H coupling constants of
about 16 Hz, corresponding to the vinylic protons of the
alkenyl ligands, and a broad signal at about 5.5 ppm,
due to the protons of the coordinated water molecule.
The 31P{1H} NMR spectra contain singlets at about -36
ppm, indicating that the phosphine ligands in the
intermediates are mutually trans disposed, as in the
starting compounds and in the reaction products.
The stability of cationic imine-vinylidene complexes
of formula [OsCl(dCdCHPh)(NHdCR2)L(PiPr3)2][CF3-
SO3] is highly dependent upon the nature of the L
ligands. Thus, in contrast with 9 and 10, the related
acetonitrile derivatives [OsCl(dCdCHPh)(NHdCR2)(CH3-
(36) Complex 9 crystallizes with a tetrahydrofuran molecule. A
careful analysis of intermolecular distances and angles suggests
intermolecular interactions between the hydrogen atoms of the water
and imine ligands and the oxygen atoms of the tetrahydrofuran and
triflate.
CN)(PiPr3)2][CF3SO3] [CR2 ) CMe2 (13), C(CH2)4CH2

5460 Organometallics, Vol. 19, No. 25, 2000
Castarlenas et al.
(14)] are stable at room temperature in the solid state
and in solution of dichloromethane. Complexes 13 and
14 have been obtained as brown solids in about 60%
yield, by stirring of 3 and 4 in acetonitrile at room
temperature, according to eq 2.
compounds, species containing both functional groups
were unknown until now. This paper reports the forma-
tion of the neutral imine-vinylidene derivatives OsCl2-
(dCdCHPh}(NHdCR2)(PiPr3)2 [CR2 ) CMe2, C(CH2)4-
CH2] and the cationic imine-vinylidene derivatives
[OsCl(dCdCHPh}(NHdCR2)L(PiPr3)2][CF3SO3] [L )
H2O, CH3CN; CR2 ) CMe2, C(CH2)4CH2]. These com-
pounds are formed by a novel reaction, the hydrogen
transfer from alkenyl ligands to azavinylidene groups.
The reaction takes place in another class of interesting
organometallic complexes, six-coordinate neutral and
cationic alkenyl-azavinylidene-osmium(IV) intermedi-
ates of the types Os{(E)-CHdCHPh}Cl2(dNdCR2)-
(PiPr3)2 and [Os{(E)-CHdCHPh}Cl(dNdCR2)L(P-
iPr3)2][CF3SO3] [L ) H2O, CH3CN; CR2 ) CMe2,
C(CH2)4CH2], which have also been characterized.
Complexes OsCl2(dCdCHPh}(NHdCR2)(PiPr3)2 and
[OsCl(dCdCHPh}(NHdCR2)(H2O)(PiPr3)2][CF3SO3] are
octahedral with the imine groups situated cis to the
chlorine ligand and the water molecule, respectively. As
a consequence of the high electronegativity of the
chlorine and oxygen atoms, this disposition gives rise
to intramolecular Cl‚‚‚H-N and O‚‚‚H-N hydrogen
bonds, between the N-H hydrogen atoms of the imines
and the chlorine ligand or water molecule. These
interactions are manifested by short Cl‚‚‚H (2.366 Å)
and O‚‚‚H (2.36 Å) separations and Cl-Os-N [77.34-
(18)°] and N-Os-O [78.3(2)°] angles largely deviated
from the ideal value of 90° for a cis arrangement.
In conclusion, this study has revealed the existence
of imine-vinylidene compounds, two new examples of
N-H‚‚‚X (Cl, O) hydrogen bonds, and the novel hydro-
gen transfer reaction from alkenyl ligands to azavi-
nylidene groups.
1
In the H NMR spectra of 13 and 14 in acetone-d6 at
room temperature, the most noticeable features are
broad resonances at about 10 ppm corresponding to the
NH hydrogen atoms of the imines, singlets at about 3
ppm due to the CH3 groups of the acetonitrile ligands,
and triplets at about 2.5 ppm with H-P coupling
constants of about 2 Hz corresponding to the dCH
hydrogen atoms of the vinylidene ligands. In the 13C-
{1H} NMR spectra, the resonances due to the CR atoms
of the vinylidenes appear at 304.6 (13) and 307.4 (14)
ppm as triplets with C-P coupling constants of about
9 Hz, while the Câ atoms display singlets at 111.6 (13)
and 114.6 (14) ppm. The CdN carbon atoms of the
imines give rise to singlets at 185.7 (13) and 192.2 (14)
ppm. The 31P{1H} NMR spectra show singlets at -10.2
(13) and -7.8 (14) ppm.
Complexes 13 and 14 are formed in a manner similar
to 9 and 10, by hydrogen transfer from the styryl ligand
to the azavinylidene groups in cationic six-coordinate
styryl-azavinylidene intermediates. In fact, the addi-
tion at -20 °C of 1.2 equiv of acetonitrile to dichlo-
romethane solutions of 3 and 4 initially gives [Os{(E)-
CHdCHPh}Cl(dNdCR2)(CH3CN)(PiPr3)2][CF3SO3] (CR2
Exp er im en ta l Section
All reactions were carried out with rigorous exclusion of air
using Schlenk-tube techniques. Solvents were dried by the
usual procedures and distilled under argon prior to use. The
starting materials OsHCl2{dNdC(CH3)2}(PiPr3)2 (1) and
OsHCl2{dNdC(CH2)4CH2}(PiPr3)2 (2) were prepared by the
published method.23 1H NMR spectra were recorded at 300
MHz, and chemical shifts are expressed in ppm downfield from
Me4Si. 13C{1H} spectra were recorded at 75.4 MHz, and
chemical shifts are expressed in ppm downfield from Me4Si.
31P{1H}spectra were recorded at 121.4 MHz, and chemical
shifts are expressed in ppm downfield from 85% H3PO4.
Coupling constants, J and N, are given in hertz.
) CMe2 (15), C(CH2)4CH2 (16)], which at room temper-
ature evolve into 13 and 14. These intermediates were
characterized in solution at -20 °C by 1H, 13C{1H}, and
31P{1H} NMR spectroscopy. In the H NMR spectra in
1
dichlorometane-d2, the most noticeable resonances are
two doublets at about 11 and 5 ppm, with H-H coupling
constants of about 16 Hz, corresponding to the vinylic
protons of the styryl ligands, and a singlet at about 3.5
ppm due to the CH3 protons of the acetonitrile groups.
In the 13C{1H} NMR spectra the resonances due to the
vinylic carbon atoms of the styryl ligands appear at
about 138 (CR) and 123 (Câ). The CdN carbon atoms of
the azavinyilidene groups are observed at 155.8 (15) and
156.3 (16). The 31P{1H} NMR spectra contain singlets
at about -32 ppm.
P r ep a r a tion of [Os{(E)-CHdCHP h }Cl{dNdC(CH3)2}-
(P iP r 3)2][CF 3SO3] (3). A blue-green solution of 1 (100 mg,
0.157 mmol) in a mixture of dichloromethane (10 mL) and
acetone (0.5 mL) was treated with 40 mg (0.157 mmol) of Ag-
[CF3SO3]. The suspension was stirred for 3 h and was filtered
through Celite to eliminate the AgCl formed. The blue solution
was cooled to -25 °C, and 20 µL (0.196 mmol) of phenylacety-
lene was added. The reaction was stirred for 5 h at
a
temperature between -25 and -10 °C. The color changed to
green, and the solvent was concentrated to dryness keeping
the temperature lower than -10 °C. Addition of diethyl ether
at -50 °C yielded a green precipitate that was washed three
times with cold diethyl ether and dried in vacuo. Yield: 95
mg (71%). Anal. Calcd for C30H55NSClF3O3OsP2: C, 42.17; H,
6.48; N, 1.63; S, 3.74. Found: C, 41.83; H, 6.41; N, 1.58; S
3.77. IR (KBr, cm-1): ν(CdN) 1624 (m); νa(SO3) 1274 (s); νs-
Con clu d in g Rem a r k s
Although imine and vinylidene transition metal com-
plexes are two interesting types of organometellic

Imine-Vinylidene-Osmium(II) Derivatives
Organometallics, Vol. 19, No. 25, 2000 5461
(CF3) 1236 (s); νa(CF3) 1160 (s); νs(SO3) 1031 (s); δa(SO3) 638
152.6 (s, OsdNdC); 138.9 (t, J C-P ) 2.8, Os CHdCHPh); 138.7
(s, Cipso-Ph); 137.5 (s, Os CHdCHPh); 128.9, 127.8 and 126.8
(all s, CPh); 120.3 (c, J C-F ) 319.7., CF3); 27.6 (br, {CH2}2Cd
N); 25.5 and 24.0 (both s, CH2 Cy) 23.3 (vt, N ) 23.5, PCH);
19.0 and 18.7 (both s, PCHCH3). 31P{1H} NMR (C6D6, 20 °C):
δ -49.6 (s). MS (FAB+): m/z ) 746 (M+).
P r epar ation of OsCl2(dCdCHP h ){NHdC(CH3)2}(P iP r 3)2
(7). A green solution of 3 (100 mg, 0.117 mmol) in a mixture
of THF (10 mL) and methanol (2 mL) was treated with NaCl
(25 mg, 0.428 mmol) and was kept stirring for 3 h at room
temperature. Then the solvent was removed and dichlo-
romethane (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, which
was washed with methanol (2 × 2 mL) and pentane (3 × 3
mL) and dried in vacuo. Yield: 70 mg (80%). Anal. Calcd for
1
(s). H NMR (CD2Cl2, 20 °C): δ 7.81 (d, J H-H ) 11.7, 1H, Os-
CHdCHPh); 7.41 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 6.96 (t, J H-H
)
7.2, 1H, Hpara-Ph); 6.86 (d, J H-H ) 7.5, 2H, Hortho-Ph); 4.00 (br,
6H, {CH3}2CdN); 3.92 (dt, J H-H ) 11.7, J H-P ) 10.2, 1H, Os-
CHdCHPh); 2.82 (m, 6H, PCH); 1.37 and 1.35 (both dvt, J H-H
) 6.9, N ) 13.8, 36H, PCHCH3). 13C{1H} NMR plus APT (CD2-
Cl2, -40 °C): δ 160.6 (br, OsdNdC); 144.0 (t, J C-P ) 6.0, Os-
CHdCHPh); 137.5 (br, Os-CHdCHPh); 134.1 (s, Cipso-Ph);
127.8, 127.6 and 126.8 (all s, CPh); 120.4 (c, J C-F ) 320.0, CF3);
23.3 (vt, N ) 22.0, PCH); 19.0 and 18.8 (both s, PCHCH3); 10.6
and 8.0 (both s, {CH3}2CdN). 31P{1H} NMR (CD2Cl2, 20 °C):
δ 0.1 (s). MS (FAB+): m/z ) 705 (M+).
P r epar ation of[Os{(E)-CHdCHP h }Cl{dNdC(CH2)4CH2}-
(P iP r 3)2][CF 3SO3] (4). This complex was prepared as de-
scribed for 3 starting from 100 mg (0.147 mmol) of 2, 37 mg
(0.147 mmol) of Ag[CF3SO3], and 20 µL (0.196 mmol) of
C
29H55NCl2OsP2: C, 47.02; H, 7.48; N, 1.89. Found: C, 47.03;
H, 7.45; N, 2.02. IR (KBr, cm-1): ν(N-H) 3216 (m); ν(CdN)
1661 (s); ν(OsdCdC) 1611 (s). 1H NMR (C6D6, 20 °C): δ 11.30
(br, 1H, N-H); 7.40 (d, J H-H ) 7.5, 2H, Hortho-Ph); 7.30 (t, J H-H
) 7.5, 2H, Hmeta-Ph); 6.80 (t, J H-H ) 7.5, 1H, Hpara-Ph); 2.86
(m, 6H, PCH); 1.98 (t, J H-P ) 1.5, 1H, OsdCdCHPh); 1.67
and 1.48 (both s, 6H, {CH3}2CdN); 1.35 and 1.30 (both dvt,
J H-H ) 6.6, N ) 13.2, 36H, PCHCH3). 13C{1H}-APT NMR
(C6D6, 20 °C): δ 295.3 (t, J C-P ) 10.0, OsdC); 177.0 (s, CdN);
131.0 (s, Cipso-Ph); 127.3, 126.2 and 123.7 (all s, CPh); 113.9 (t,
J C-P ) 3.2, OsdCdC); 30.0 and 24.8 (both s, {CH3}2CdN); 23.8
(vt, N ) 22.0, PCH); 19.8 and 19.6 (both s, PCHCH3). 31P{1H}
NMR (C6D6, 20 °C): δ -21.1 (s). MS (FAB+): m/z ) 705 (M+
- HCl).
phenylacetylene. Yield: 92 mg (70%). Anal. Calcd for C33H59
-
NSClF3O3OsP2: C, 44.31; H, 6.64; N, 1.56; S, 3.57. Found: C,
43.98; H, 6.53; N, 1.48; S 3.21. IR (KBr, cm-1): ν(CdN) 1617
(m); νa(SO3) 1271 (s); νs(CF3) 1235 (s); νa(CF3) 1159 (s); νs(SO3)
1
1030 (s); δa(SO3) 637 (s). H NMR (CD2Cl2, 20 °C): δ 7.84 (d,
J H-H ) 10.8, 1H, Os-CHdCHPh); 7.39 (t, J H-H ) 7.2, 2H,
H
meta-Ph); 6.96 (t, J H-H ) 7.2, 1H, Hpara-Ph); 6.83 (d, J H-H )
7.5, 2H, Hortho-Ph); 4.30 (br, 4H, {CH2}2CdN); 3.92 (br, Os-
CHdCHPh); 2.84 (m, 6H, PCH); 1.8-1.5 (m, 6H, Cy); 1.37 and
1.35 (both dvt, J H-H ) 6.9, N ) 13.8, 36H, PCHCH3). 13C{1H}
NMR (CD2Cl2, -40 °C): δ 161.9 (br, OsdNdC); 143.6 (t, J C-P
) 5.0, Os-CHdCHPh); 137.5 (br, Os-CHdCHPh); 134.2 (s,
C
ipso-Ph); 128.9, 127.8 and 126.8 (all s, CPh); 120.3 (c, J C-F )
319.7, CF3); 36.1 and 33.8 (both s, {CH2}2CdN); 24.4, 21.6 and
18.3 (all s, CH2 Cy); 22.7 (vt, N ) 24.0, PCH); 19.0 and 18.7
(both s, PCHCH3). 31P{1H} NMR (CD2Cl2, 20 °C): δ 2.1 (s).
MS (FAB+): m/z ) 746 (M+).
P r ep a r a tion of OsCl2(dCdCHP h ){NHdC(CH 2)4CH2}-
(P iP r 3)2 (8). This complex was prepared as described for 7
starting from 125 mg (0.140 mmol) of 4 and 25 mg (0.428
mmol) of NaCl. Yield: 85 mg (78%). Anal. Calcd for C32H59
-
P r ep a r a tion of Os{(E)-CHdCHP h }Cl2{dNdC(CH3)2}-
(P iP r 3)2 (5). A green solution of 3 (100 mg, 0.117 mmol), in 8
mL of THF at -30 °C, was treated with NaCl (25 mg, 0.428
mmol) and was kept stirring for 3 h at this temperature. The
color changed to orange, and the solvent was concentrated to
dryness at -30 °C. Then 8 mL of toluene was added to
eliminate by filtration the NaSO3CF3 formed and the excess
of NaCl. After the toluene was removed again at -30 °C,
addition of pentane at -50 °C yielded an orange precipitate,
which was washed three times with cold pentane and dried
in vacuo. Yield: 70 mg (80%). Anal. Calcd for C29H55NCl2-
OsP2: C, 47.02; H, 7.48; N, 1.89. Found: C, 46.74; H, 7.48; N,
1.75. IR (KBr, cm-1): ν(CdN) 1667 (m). 1H NMR (C6D6, 20
°C): δ 11.97 (d, J H-H ) 16.5, 1H, Os-CHdCHPh); 7.32 (t, J H-H
) 7.5, 2H, Hmeta-Ph); 7.04 (d, J H-H ) 7.8, 2H, Hortho-Ph); 6.70 (t,
J H-H ) 7.5, 1H, Hpara-Ph); 4.93 (d, J H-H ) 16.5, 1H, Os-CHd
CHPh); 3.90 (br, 6H, {CH3}2CdN); 2.91 (m, 6H, PCH); 1.32
and 1.28 (both dvt, J H-H ) 6.5, N ) 12.3, 36H, PCHCH3). 13C-
{1H} NMR (CDCl3, 20 °C): δ 150.7 (s, OsdNdC); 139.4 (s, Os-
CHdCHPh); 133.4 (J C-P ) 3.5, Os-CHdCHPh); 129.0 (s,
NCl2OsP2: C, 49.22; H, 7.62; N, 1.79. Found: C, 49.04; H, 7.54;
N, 1.72. IR (KBr, cm-1): ν(N-H) 3202 (m); ν(CdN) 1656 (m);
1
ν(OsdCdC) 1610 (s). H NMR (C6D6, 20 °C): δ 11.07 (br, 1H,
N-H); 7.09 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 6.94 (d, J H-H ) 7.5,
2H, Hortho-Ph); 6.67 (t, J H-H ) 7.5, 1H, Hpara-Ph); 2.78 (m, 6H,
PCH); 2.59 and 2.48 (both m, 4H, {CH2}2CdN); 1.82 (t, J H-P
) 2.0, 1H, OsdCdCHPh); 1.71 (m, 2H, Cy); 1.58 (m, 4H, Cy);
1.31 and 1.27 (both dvt, J H-H ) 6.9, N ) 12.9, 36H, PCHCH3).
13C{1H}-APT NMR (C6D6, 20 °C): δ 295.1 (t, J C-P ) 8.3, Osd
C); 182.7 (s, CdN); 130.2 (s, Cipso-Ph); 127.3, 125.7, and 122.8
(all s, CPh); 113.3 (t, J C-P ) 3.7, OsdCdC); 42.9, 34.4, 26.2,
25.5, and 24.2 (all s, CH2 Cy); 23.4 (vt, N ) 22.1, PCH); 19.6
and 19.4 (both s, PCHCH3). 31P{1H} NMR (C6D6, 20 °C): δ
-20.8 (s). MS (FAB+): m/z ) 745 (M+ - HCl).
P r ep a r a tion of [OsCl(dCdCHP h ){NHdC(CH3)2}(H2O)-
(P iP r 3)2][CF 3SO3] (9). A green solution of 3 (125 mg, 0.146
mmol) in THF (10 mL) at -20 °C was treated with H2O (25
µL, 1.39 mmol) and was kept in the freezer at -20 °C for 3
days. The color changed to red, and after the solvent was
removed at -20 °C, addition of cold diethyl ether yielded a
mycrocristalline red solid, which was washed with diethyl
ether (3 × 2 mL) and dried in vacuo. Yield: 90 mg (70%). Anal.
Calcd for C30H57NSClF3O4OsP2: C, 41.30; H, 5.59; N, 1.61; S,
3.67. Found: C, 41.12; H, 5.34; N, 1.72; S, 3.72. IR (KBr, cm-1):
ν(H2O) 3254 (br); ν(N-H) overlapped by H2O; ν(CdN) 1662
(s); ν(OsdCdC) 1617 (s); νa(SO3) 1297 (s); νs(CF3) 1234 (s); νa-
(CF3) 1167 (s); νs(SO3) 1028 (s); δa(SO3) 639 (s). 1H NMR (CD2-
Cl2, -60 °C): δ 10.42 (br, 1H, N-H); 7.15 (t, J H-H ) 7.5, 2H,
C
ipso-Ph); 128.2, 127.3 and 127.0 (all s, CPh); 23.7 (vt, N ) 22.0,
PCH); 19.2 and 19.1 (both s, PCHCH3); 17.8 (br, {CH3}2Cd
N). 31P{1H} NMR (C6D6, 20 °C): δ -51.4 (s). MS (FAB+): m/z
) 706 (M+ - Cl).
P r epar ation ofOsCl2{(E)-CHdCHP h }{dNdC(CH2)4CH2}-
(P iP r 3)2 (6). This complex was prepared as described for 5
starting from 125 mg (0.140 mmol) of 4 and NaCl (25 mg, 0.428
mmol). Yield: 90 mg (82%). Anal. Calcd for C32H59NCl2OsP2:
C, 49.22; H, 7.62; N, 1.79. Found: C, 49.64; H, 7.50; N, 1.86.
1
IR (KBr, cm-1): ν(CdN) 1656 (m). H NMR (C6D6, 20 °C): δ
H
meta-Ph); 6.86 (d, J H-H ) 7.5, 2H, Hortho-Ph); 6.74 (t, J H-H )
7.5, 1H, Hpara-Ph); 5.45 (br, 2H, H2O); 2.59 (m, 6H, PCH); 2.57
and 2.25 (both s, 6H, {CH3}2CdN); 2.45 (br, 1H, OsdCd
CHPh); 1.4-1.2 (br, 36H, PCHCH3). 13C{1H} NMR (CD2Cl2,
-30 °C): δ 299.0 (t, J C-P ) 10.6, OsdC); 185.2 (s, CdN); 129.0,
127.3, 125.1, and 123.5 (all s, CPh); 120.1 (c, J C-F ) 316.6, CF3);
112.6 (s, OsdCdC); 28.8 and 27.1 (both s, {CH3}2CdN); 23.5
11.62 (d, J H-H ) 16.0, 1H, Os-CHdCHPh); 7.35 (t, J H-H
)
7.2, 2H, Hmeta-Ph); 6.85 (d, J H-H ) 7.5, 2H, Hortho-Ph); 6.73 (t,
J H-H ) 7.2, 1H, Hpara-Ph); 4.80 (d, J H-H ) 16.8, 1H, Os-CHd
CHPh); 4.6 (br, 4H, {CH2}2CdN); 3.01 (m, 6H, PCH); 1.8-1.5
(m, 6H, Cy); 1.44 and 1.39 (both dvt, J H-H ) 6.5, N ) 13.2,
36H, PCHCH3). 13C{1H} NMR plus APT (CDCl3, 20 °C): δ

5462 Organometallics, Vol. 19, No. 25, 2000
Castarlenas et al.
(br, PCH); 19.2 and 18.6 (both s, PCHCH3). 31P{1H} NMR (CD2-
Cl2, -60 °C): δ -15.3 (s). MS (FAB+): m/z ) 705 (M+ - H2O).
P r ep a r a tion of [OsCl(dCdCHP h ){NHdC(CH2)4CH2}-
(NCCH3)(P iP r 3)2][CF 3SO3] (14). This complex was prepared
as described for 13 starting from 125 mg (0.140 mmol) of 4.
Yield: 85 mg (64%). Anal. Calcd for C35H62N2SClF3O3OsP2: C,
44.94; H, 6.68; N, 2.99; S, 3.43. Found: C, 44.75; H, 6.55; N,
2.82; S, 3.31. IR (KBr, cm-1): ν(N-H) 3246 (br); ν(CtN) 2303
(w); ν(CdN) 1686 (s); ν(OsdCdC) 1626 (s); νa(SO3) 1261 (s);
νs(CF3) 1223 (s); νa(CF3) 1149 (s); νs(SO3) 1031 (s); δa(SO3) 637
P r ep a r a tion of [OsCl2(dCdCHP h ){NHdC(CH2)4CH2}-
(H2O)(P iP r 3)2][CF 3SO3] (10). This complex was prepared as
described for 9 starting from 125 mg (0.140 mmol) of 4 and 25
µL of H2O (1.39 mmol). Yield: 95 mg (74%). Anal. Calcd for
C33H61NSClF3O4OsP2: C, 43.43; H, 6.74; N, 1.53. Found: C,
43.14; H, 6.42; N, 1.59. IR (KBr, cm-1): ν(H2O) 3237 (br); ν-
(N-H) overlapped by the ν(H2O); ν(CdN) 1655 (s); ν(OsdCd
C) 1617 (s); νa(SO3) 1302 (s); νs(CF3) 1237 (s); νa(CF3) 1164 (s);
νs(SO3) 1029 (s); δa(SO3) 638 (s). 1H NMR (CD2Cl2, -40 °C): δ
10.30 (br, 1H, N-H); 7.13 (t, J H-H ) 7.2, 2H, Hmeta-Ph); 6.87
(d, J H-H ) 7.2, 2H, Hortho-Ph); 6.72 (t, J H-H ) 7.2, 1H, Hpara-Ph);
5.30 (br, 2H, H2O); 2.42 (br, 1H, OsdCdCHPh); 2.84 and 2.38
(both m, 4H, {CH2}2CdN); 2.60 (m, 6H, PCH); 1.73 (m, 2H,
Cy); 1.60 (m, 4H, Cy); 1.28 (br, 36H, PCHCH3). 13C{1H} NMR
(CD2Cl2, -40 °C): δ 299.1 (t, J C-P ) 10.5, OsdC); 190.0 (s,
CdN); 129.1, 127.4, 125.0, and 122.0 (all s, CPh); 112.6 (s, Osd
CdC); 40.4, 35.4, 26.4, 26.1, and 24.1 (all s, Cy); 24.1 (br, PCH);
20-18 (br, PCHCH3). 31P{1H} NMR (CD2Cl2, -40 °C): δ -15.0
(s). MS (FAB+): m/z ) 746 (M+ - H2O).
Rea ction of 3 w ith H2O: P r ep a r a tion of [Os{(E)-CHd
CHP h }Cl{dNdC(CH3)2}(H2O)(P iP r 3)2][CF 3SO3] (11). A so-
lution of 3 (25 mg, 0.029 mmol) in 0.5 mL of dichloromethane-
d2 in an NMR tube at -90 °C was treated with H2O (1 µL,
0.055 mmol). The NMR tube was sealed under argon, and
measurements were made immediately. 1H NMR (CD2Cl2, -90
°C): δ 10.65 (d, J H-H ) 15.6, 1H, Os-CHdCHPh); 7.30 (t, J H-H
) 7.5, 2H, Hmeta-Ph); 6.94 (d, J H-H ) 7.5, 2H, Hortho-Ph); 6.84 (t,
1
(s). H NMR (acetone-d6, 20 °C): δ 10.18 (br, 1H, N-H); 7.31
(t, J H-H ) 7.5, 2H, Hmeta-Ph); 6.99 (d, J H-H ) 7.2, 2H, Hortho-Ph);
6.92 (t, J H-H ) 7.5, 1H, Hpara-Ph); 3.24 (s, 3H, NCCH3); 2.91
and 2.81 (both m, 4H, {CH2}2CdN); 2.79 (m, 6H, PCH); 2.63
(t, J H-P ) 2.0, 1H, OsdCdCHPh); 1.86 (m, 2H, Cy); 1.72 (m,
4H, Cy); 1.34 and 1.32 (both dvt, J H-H ) 6.9, N ) 13.5, 36H,
PCHCH3). 13C{1H}-APT NMR (acetone-d6, 20 °C): δ 307.4 (t,
J C-P ) 9.1, OsdC); 192.2 (s, CdN); 136.6 (s, Cipso-Ph); 129.5,
128.2, and 126.2 (all s, CPh); 127.9 (s, NtC-CH3); 114.6 (s,
OsdCdC); 43.4, 36.4, 27.6, 27.1, and 25.0 (all s, CH2 Cy); 24.9
(vt, N ) 23.4, PCH); 20.5 and 19.7 (both s, PCHCH3); 8.8 (s,
N/CtCH3). 31P{1H} NMR (acetone-d6, 20 °C): δ -7.8 (s). MS
(FAB+): m/z ) 787 (M+); 746 (M+ - NCCH3).
Rea ction of 3 w ith CH 3CN: P r ep a r a tion of [Os{(E)-
CH dCH P h }Cl{dNdC(CH 3)2}(NCCH 3)(P iP r 3)2][CF 3SO3]
(15). A solution of 3 (25 mg, 0.029 mmol) in 0.5 mL of
dichloromethane-d2 in a NMR tube at -20 °C was treated with
CH3CN (2 µL, 0.035 mmol). The NMR tube was sealed under
1
argon, and measurements were made immediately. H NMR
(CD2Cl2, -20 °C): δ 10.93 (d, J H-H ) 16.0, 1H, Os-CHd
CHPh); 7.38 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 7.08 (d, J H-H ) 7.5,
2H, Hortho-Ph); 6.88 (t, J H-H ) 7.5, 1H, Hpara-Ph); 5.22 (d, J H-H
) 16.0, 1H, Os-CHdCHPh); 3.63 and 3.56 (both s, 6H,
{CH3}2CdN); 3.44 (s, 3H, NCCH3); 2.86 (m, 6H, PCH); 1.40
(br, 36H, PCHCH3). 13C{1H} NMR (CD2Cl2, -20 °C): δ 155.9
(s, CdN); 138.2 (s, NtC-CH3); 137.9 (s, Os-CHdCHPh);
137.2 (s, Cipso-Ph); 127.8, 127.4, and 127.0 (all s, CPh); 123.1 (s,
Os-CHdCHPh); 121.1 (c, J C-F ) 318.2, CF3); 22.0 (vt, N )
23.0, PCH); 19.0 and 18.7 (both s, PCHCH3); 5.7 (s, NtC-
CH3); 4.2 and 3.9 (both s, ({CH3}2CdN). 31P{1H} NMR (CD2-
Cl2, -20 °C): δ -36.4 (s).
J H-H ) 7.5, 1H, Hpara-Ph); 5.63 (br, 2H, H2O); 4.72 (d, J H-H
)
15.6, 1H, Os-CHdCHPh); 3.88 and 3.82 (both s, 6H, {CH3}2Cd
N); 2.51 (m, 6H, PCH); 1.21 (br, 36H, PCHCH3). 31P{1H} NMR
(CD2Cl2, -90 °C): δ -36.0 (s).
Rea ction of 4 w ith H2O: P r ep a r a tion of [Os{(E)-CHd
CHP h }Cl{dNdC(CH2)4CH2}(H2O)(P iP r 3)2][CF 3SO3] (12).
This complex was prepared as described for 11 starting from
25 mg (0.028 mmol) of 4 and 1 µL (0.055 mmol) of H2O. 1H
NMR (CD2Cl2, -90 °C): δ 10.70 (d, J H-H ) 15.9, 1H, Os-CHd
CHPh); 7.37 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 7.02 (d, J H-H ) 7.5,
2H, Hortho-Ph); 6.90 (t, J H-H ) 7.5, 1H, Hpara-Ph); 5.71 (br, 2H,
H2O); 4.81 (d, J H-H ) 15.9, 1H, Os-CHdCHPh); 3.9-3.7 (m,
4H, {CH2}2CdN); 2.77 (m, 6H, PCH); 2-1 (m, 6H, Cy); 1.29
(br, 36H, PCHCH3). 31P{1H} NMR (CD2Cl2, -90 °C): δ -35.6
(s).
Rea ction of 4 w ith CH3CN: P r ep a r a tion of Os{(E)-
CH dCH P h }Cl{dNdC(CH 2)4CH 2}(NCCH 3)(P iP r 3)2][CF 3-
SO3] (16). This complex was prepared as described for 15
starting from 25 mg (0.028 mmol) of 4 and CH3CN (2 µL, 0.035
mmol). 1H NMR (CD2Cl2, -20 °C): δ 10.72 (d, J H-H ) 15.9,
1H, Os-CHdCHPh); 7.35 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 6.95
(d, J H-H ) 7.5, 2H, Hortho-Ph); 6.88 (t, J H-H ) 7.5, 1H, Hpara-Ph);
5.04 (d, J H-H ) 15.9, 1H, Os-CHdCHPh); 3.64 and 3.57 (both
s, 4H, {CH2}2CdN); 3.16 (s, 3H, NCCH3); 2.73 (m, 6H, PCH);
2-1 (m, 6H, Cy); 1.35 (br, 36H, PCHCH3). 13C{1H} NMR (CD2-
Cl2, -20 °C): δ 156.3 (s, CdN); 138.2 (s, Os-CHdCHPh); 137.5
(s, Cipso-Ph); 135.3 (s, NtC-CH3); 127.5, 127.0, and 126.9 (all
s, CPh); 123.3 (s, Os-CHdCHPh); 121.1 (c, J C-F ) 318.2, CF3);
26.2, 26.0, 16.5, 14.7 (all s, Cy); 22.9 (vt, N ) 23.0, PCH); 18.8
and 18.7 (both s, PCHCH3); 4.9 (s, NtC-CH3). 31P{1H} NMR
(CD2Cl2, -20 °C): δ -36.6 (s).
Cr yst a l Da t a for OsCl2(dCdCH P h ){NH dC(CH 3)2}-
(P iP r 3)2 (7) a n d [OsCl(dCdCHP h ){NHdC(CH3)2}(H2O)-
(P iP r 3)2][CF 3SO3] (9). Crystals suitable for X-ray diffraction
analysis were mounted onto a glass fiber and transferred to
an Bruker-Siemens-STOE AED-2 (7, T ) 298.0(2) K) and
Bruker-Siemens P-4 (9, T ) 173.0(2) K) automatic diffracto-
meters (Mo KR radiation, graphite monocromator, λ ) 0.71073
Å). Accurate unit cell parameters were determined by least-
squares fitting from the settings of high-angle reflections. Data
were collected by the ω/2θ scan method. Lorentz and polariza-
tion corrections were applied. Decay was monitored by mea-
suring three standards throughout data collection. Corrections
for decay and absortion (semiempirical ψ-scan method) were
also applied.
P reparation of[OsCl(dCdCHP h){NHdC(CH3)2}(NCCH3)-
(P iP r 3)2][CF 3SO3] (13). A green solution of 3 (125 mg, 0.146
mmol) in CH3CN (10 mL) was stirred for 4 h at room
temperature. The color changed to brown. The solvent was
concentrated to ca. 1 mL, and addition of diethyl ether yielded
a brown precipitate, which was decanted, washed twice with
diethyl ether, and dried in vacuo. Yield: 80 mg (61%). Anal.
Calcd for C32H58N2SClF3O3OsP2: C, 42.92; H, 6.53; N, 3.13;
S, 3.58. Found: C, 42.81; H, 6.37; N, 3.22; S, 3.41. IR (KBr,
cm-1): ν(N-H) 3240 (br); ν(CtN) 2301 (w); ν(CdN) 1687 (s);
ν(OsdCdC) 1618 (s); νa(SO3) 1260 (s); νs(CF3) 1223 (s); νa(CF3)
1
1154 (s); νs(SO3) 1031 (s); δa(SO3) 638 (s). H NMR (acetone-
d6, 20 °C): δ 10.17 (br, 1H, N-H); 7.30 (t, J H-H ) 7.5, 2H,
H
meta-Ph); 7.00 (d, J H-H ) 7.5, 2H, Hortho-Ph); 6.90 (t, J H-H )
7.5, 1H, Hpara-Ph); 3.22 (s, 3H, NCCH3); 2.81 (m, 6H, PCH);
2.65 and 2.52 (both s, 6H, {CH3}2CdN); 2.62 (t, J H-P ) 2.4,
1H, OsdCdCHPh); 1.37 and 1.35 (both dvt, J H-H ) 6.9, N )
13.5, 36H, PCHCH3). 13C{1H}-APT NMR (acetone-d6, 20 °C):
δ 304.6 (t, J C-P ) 9.2, OsdC); 185.7 (s, CdN); 130.7 (s, Cipso-Ph);
126.7, 125.4 and 123.6 (all s, CPh); 125.1 (s, NtC-CH3); 121.1
(c, J C-F ) 316.6, CF3); 111.6 (s, OsdCdC); 29.1 and 24.1 (both
s, {CH3}2CdN); 22.0 (vt, N ) 23.3, PCH); 17.5 and 17.2 (both
s, PCHCH3); 1.9 (s, NtC-CH3). 31P{1H} NMR (acetone-d6, 20
°C): δ -10.2 (s). MS (FAB+): m/z ) 706 (M+ - NCCH3).

Imine-Vinylidene-Osmium(II) Derivatives
Organometallics, Vol. 19, No. 25, 2000 5463
The structures were solved by Patterson methods and
refined by full matrix least-squares on F2 (7 and 9).37 For 7,
non hydrogen atoms were anisotropically refined, and the
hydrogen atoms were observed or included at idealized posi-
tions. The imine and vinylidene hydrogen atoms H(01) and
H(5) were located in the difference Fourier maps and refined
isotropically. For 9, the triflate anion and the THF solvent
molecules were observed disordered. Both molecules were
refined with two moieties, complementary occupancy factors,
isotropic atoms, and restrained geometry.37 The rest of the non-
hydrogen atoms were anisotropically refined, and hydrogen
atoms were observed or included at idealized positions. In this
case, only the water hydrogen atoms could be refined freely
as isotropic atoms.
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.
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 7 and 9. This
material is available free of charge via the Internet at
http://pubs.acs.org.
(37) Sheldrick, G. M. SHELX-97; Go¨ttingen, 1997.
OM0005295