One-pot synthesis for osmium(II) azavinylidene-carbyne and azavinylidene-alkenylcarbyne complexes starting from an osmium(II) hydride-azavinylidene compound

Article abstract of DOI:10.1021/om0101386

Treatment at room temperature of the complex OsHCl₂(=N=CMe₂)(PⁱPr₃)₂ (1) with Ag-[CF₃SO₃] and the subsequeny stirring of the resulting solution under an acetylene atmosphere gives the azavinylidene-carbyne derivative [OsCl(=N=CMe₂)(≡CCH₃)PⁱPr₃] [CF₃SO₃] (2). The related complexes [OsCl(=N=CMe₂)(≡CCH₂R)(PⁱPr₃) ₂] [CF₃SO₃] (R = Cy (3), (CH₂)₂-CH₃ (4)) have been prepared by reaction of 1 with Ag[CF₃SO₃] and cyclohexylacetylene or 1-pentyne. The structure of 2 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 phosphines and inequivalent angles within the Y-shaped equatorial plane. The azavinylidene coordinates in a bent fashion with an Os-N-C angle of 152.0(8)°. Complexes 2-4 react with MeLi to afford the five-coordinate azavinylidene-vinylidenes OsCl(=N=CMe₂)(=C=CHR)(PⁱPr₃)₂ (R = H (5), Cy (6), (CH₂)₂CH₃ (7)), as result of the deprotonation of the βCH₂ group of the carbyne ligands in 2-4. The formation of 2-4 involves azavinylidene-alkenyl and imine-vinylidene intermediates. In agreement with this, it is also reported that, at -25 °C, the addition of cyclohexylacetylene to the solution resulting from the treatment of 1 with Ag{CF₃SO₃] affords [OS{(E)-CH=CHCy}Cl(=N=CMe₂)(PⁱPr₃)₂] [CF₃SO₃] (8), where the H_β atom of the alkenyl ligand interacts with the osmium atom to form an agostic bond. At -30 °C, the addition of NaCl to tetrahydrofuran solutions of 8 gives OsCl₂(=C=CHCy)(NH=CMe₂)Pⁱ Pr₃)₂ (9), which evolves into 6 in solution at room temperature. Complex 1 also reacts with Ag[CF₃SO₃] and 2-methyl-1-buten-3-yne. The reaction leads to the azavinylidene-alkenylcarbyne [OsCl(=N=CMe₂)(≡CCH=CMe₂)(ⁱ- Pr₃)₂][CF₃SO₃] (10), which by deprotonation with MeLi yields the azavinylidene-alkenylvinylidene OsCl(=N=CMe₂){=C=CHC(Me)=CH₂=CH₂}(Pⁱ Pr₃)₂ (11). The formation of 10 proceeds similarly to those of 2-4. Thus, it has been observed that, at -25 °C, the addition of 2-methyl-1-buten-3-yne to the solution resulting from the treatment of 1 with Ag[CF₃SO₃] gives [Os-{(E)-CH=CHC(Me)=CMe₂}Cl(=N=CMe₂)(PⁱPr₃ )₂][CF₃SO₃] (12), which in solution at room temperature evolves into 10. The complexes [OsCl(=N=CMe₂)(≡CCH=CPhR)(Pⁱ Pr₃)₂] [CF₃-SO₃] (R = H (13), CH₃ (14), Ph (15)) have been prepared by reaction of 1 with Ag[CF₃SO₃] and 1-phenyl-2-propyn-1-ol, 2-phenyl-3-butyn-2-ol, and 1,1-diphenyl-2-propyn-1-ol, respectively. The deprotonation of 14 with MeLi affords (OsCl(=N=CMe₂){=C=CHC(Ph)=CH₂}-(Pⁱ Pr³)₂ (15).

Full text of DOI:10.1021/om0101386

Organometallics 2001, 20, 3283-3292
3283
On e-P ot Syn th esis for Osm iu m (II)
Aza vin ylid en e-Ca r byn e a n d
Aza vin ylid en e-Alk en ylca r byn e Com p lexes Sta r tin g fr om
a n Osm iu m (II) Hyd r id e-Aza vin ylid en e Com p ou n d
Ricardo Castarlenas, Miguel A. Esteruelas,* 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
Received February 20, 2001
Treatment at room temperature of the complex OsHCl2(dNdCMe2)(PiPr3)2 (1) with Ag-
[CF3SO3] and the subsequent stirring of the resulting solution under an acetylene atmosphere
gives the azavinylidene-carbyne derivative [OsCl(dNdCMe2)(tCCH3)(PiPr3)2][CF3SO3] (2).
The related complexes [OsCl(dNdCMe2)(tCCH2R)(PiPr3)2][CF3SO3] (R ) Cy (3), (CH2)2-
CH3 (4)) have been prepared by reaction of 1 with Ag[CF3SO3] and cyclohexylacetylene or
1-pentyne. The structure of 2 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 phosphines and inequivalent angles within the Y-shaped equatorial
plane. The azavinylidene coordinates in a bent fashion with an Os-N-C angle of 152.0(8)°.
Complexes 2-4 react with MeLi to afford the five-coordinate azavinylidene-vinylidenes
OsCl(dNdCMe2)(dCdCHR)(PiPr3)2 (R ) H (5), Cy (6), (CH2)2CH3 (7)), as a result of the
deprotonation of the â-CH2 group of the carbyne ligands in 2-4. The formation of 2-4
involves azavinylidene-alkenyl and imine-vinylidene intermediates. In agreement with
this, it is also reported that, at -25 °C, the addition of cyclohexylacetylene to the solution
resulting from the treatment of 1 with Ag[CF3SO3] affords [Os{(E)-CHdCHCy}Cl(dNd
CMe2)(PiPr3)2][CF3SO3] (8), where the Hâ atom of the alkenyl ligand interacts with the
osmium atom to form an agostic bond. At -30 °C, the addition of NaCl to tetrahydrofuran
solutions of 8 gives OsCl2(dCdCHCy)(NHdCMe2)(PiPr3)2 (9), which evolves into 6 in solution
at room temperature. Complex 1 also reacts with Ag[CF3SO3] and 2-methyl-1-buten-3-yne.
The reaction leads to the azavinylidene-alkenylcarbyne [OsCl(dNdCMe2)(tCCHdCMe2)(Pi-
Pr3)2][CF3SO3] (10), which by deprotonation with MeLi yields the azavinylidene-alkenylvin-
ylidene OsCl(dNdCMe2){dCdCHC(Me)dCH2}(PiPr3)2 (11). The formation of 10 proceeds
similarly to those of 2-4. Thus, it has been observed that, at -25 °C, the addition of 2-methyl-
1-buten-3-yne to the solution resulting from the treatment of 1 with Ag[CF3SO3] gives [Os-
{(E)-CHdCHC(Me)dCMe2}Cl(dNdCMe2)(PiPr3)2][CF3SO3] (12), which in solution at room
temperature evolves into 10. The complexes [OsCl(dNdCMe2)(tCCHdCPhR)(PiPr3)2][CF3-
SO3] (R ) H (13), CH3 (14), Ph (15)) have been prepared by reaction of 1 with Ag[CF3SO3]
and 1-phenyl-2-propyn-1-ol, 2-phenyl-3-butyn-2-ol, and 1,1-diphenyl-2-propyn-1-ol, respec-
tively. The deprotonation of 14 with MeLi affords OsCl(dNdCMe2){dCdCHC(Ph)dCH2}-
(PiPr3)2 (15).
In tr od u ction
3-ynes. The key intermediates of these reactions are
dihydrogen-vinylidene species, which evolve by elec-
trophilic attack of the acidic hydrogen proton of the
dihydrogen on the Câ atom of the vinylidene.2
The behavior of the complex OsH2Cl2(PiPr3)2 in the
presence of alkynes cannot be extrapolated to other
osmium compounds containing two hydrogen atoms
bonded to the metallic center. Up until now, in addition
to OsH2Cl2(PiPr3)2, the reactivity of three complexes has
been studied: the dihydrogen OsCl2(η2-H2)(CO)(PiPr3)2,3
the neutral seven-coordinate dihydride OsH2(κ2-O2-
The synthesis of Fischer type carbyne complexes has
been traditionally a laborious process, which has in-
volved the formation of transition-metal-bonded sp2- or
sp-hybridized carbon atoms and their subsequent trans-
formation into sp carbyne carbon atoms.1
In 1993, we showed that the carbynes OsHCl2(tC-
CH2R)(PiPr3)2 and alkenylcarbynes OsHCl2(tCCHd
CR2)(PiPr3)2 can be prepared in a one-pot synthesis by
treatment of the dihydride-dichloro complex OsH2-
Cl2(PiPr3)2 with terminal alkynes, alkynols, and 1-en-
(2) Espuelas, J .; Esteruelas, M. A.; Lahoz, F. J .; Oro, L. A.; Ruiz, N.
J . Am. Chem. Soc. 1993, 115, 4683.
(3) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Valero, C.;
Zeier, B. J . Am. Chem. Soc. 1995, 117, 7935.
(1) Fischer, H. In Carbyne Complexes; Fischer, H., Hofmann, P.,
Kreissl, F. R., Schrock, R. R., Schubert, U., Weiss, K., Ed.; Verlags-
gesellschaft mbH: Weinheim, Germany, 1988; pp 2-38.
10.1021/om0101386 CCC: $20.00 © 2001 American Chemical Society
Publication on Web 06/15/2001

3284 Organometallics, Vol. 20, No. 15, 2001
Castarlenas et al.
CCH3){κ1-OC(O)CH3}(PiPr3)2,4 and the cationic seven-
coordinate dihydride [OsH2(κ2-O2CCH3)(H2O)(PiPr3)2]+,5
and between them serious differences of behavior are
observed. It appears that the formed organometallic
compound is a result of a sophisticated combination of
electronic factors involving the metal and the alkyne.
Thus, the dihydrogen complex OsCl2(η2-H2)(CO)(PiPr3)2
reacts with phenylacetylene to give the carbene deriva-
tive OsCl2(dCHCH2Ph)(CO)(PiPr3)2,3 whereas the neu-
tral dihydride OsH2(κ2-O2CCH3){κ1-OC(O)CH3}(PiPr3)2
affords the hydride-vinylidene OsH(κ2-O2CCH3){dCd
CHC(CH3)dCH2}(PiPr3)2 in the presence of 2-methyl-
1-buten-3-yne,4 and the cation [OsH2(κ2-O2CCH3)(H2O)-
(PiPr3)2]+ gives hydride-osmacyclopropenes, hydride-
carbynes,5 or mixtures of both types of compounds
depending upon the nature of the alkyne.6
In contrast to the osmium compounds containing two
hydrogen atoms bonded to the metal, the chemistry of
osmium monohydrides in the presence of terminal
alkynes is very clear. Via vinylidene7 or π-alkyne8
intermediates, they afford alkenyl derivatives.9 When
alkynols are used, alkenylcarbene compounds are also
obtained.10 However, the formation of carbyne com-
plexes has not been observed.
Azavinylidene complexes are an interesting class of
transition-metal compounds containing an M-N double
bond.11,12 Some of them have even been proposed as
intermediates in the catalytic and stoichiometric reduc-
tion of nitriles13,11s,x and in the ammoxidation of
propylene.11o Hydride-azavinylidene complexes are
very rare, and only two mononuclear species had been
reported before 2000: the five-coordinate d6 derivatives
MH(dNdCPh2)(CO)(PiPr3)2 (M ) Ru,14 Os15).
We have recently shown that the dihydride-dichloro
complex OsH2Cl2(PiPr3)2 reacts, in a one-pot synthesis,
not only with terminal alkynes but also with oximes.
The reactions lead to the six-coordinate d4 hydride-
azavinylidene derivatives OsHCl2(dNdCR2)(PiPr3)2,16
which are related to the carbynes OsHCl2(tCCH2R)-
(PiPr3)2 containing an azavinylidene ligand instead of
a carbyne group.
are the result of the addition of the M-H bond of the
starting materials to the carbon-carbon triple bond of
the alkyne, in agreement with the general tendency
shown by the osmium monohydride complexes. In
solution at room temperature, the azavinylidene-styryl
compounds are unstable and evolve into a novel type of
derivative, containing the imine and vinylidene func-
tional groups, by the novel hydrogen transfer reaction
from styryl groups to azavinylidene ligands.17
In this paper, we report the formation of other two
novel types of difunctional organometallic compounds,
azavinylidene-carbyne and azavinylidene-alkenyl-
(11) (a) Farmery, K.; Kilner, M.; Midcalf, C. J . Chem. Soc. A 1970,
2279. (b) Kilner, M.; Midcalf, C. J . Chem. Soc. A 1971, 292. (c) Chatt,
J .; Dosser, R. J .; King, F.; Leigh, G. J . J . Chem. Soc., Dalton Trans.
1976, 2435. (d) Erker, G.; Fro¨mberg, W.; Atwood, J . L.; Hunter, W. E.
Angew. Chem., Int. Ed. Engl. 1984, 23, 68. (e) Cramer, R. E.;
Panchanatheswaran, K.; Gilje, J . W. J . Am. Chem. Soc. 1984, 106,
1853. (f) Fro¨mberg, W.; Erker, G. J . Organomet. Chem. 1985, 280, 343.
(g) Green, M.; Mercer, R. J .; Morton, C. E.; Orpen, A. G. Angew. Chem.,
Int. Ed. Engl. 1985, 24, 422. (h) Bercaw, J . E.; Davies, D. L.;
Wolczanski, P. T. Organometallics 1986, 5, 443. (i) Bochmann, M.;
Wilson, L. M. J . Chem. Soc., Chem. Commun. 1986, 1610. (j) Latham,
I. A.; Leigh, G. J .; Huttner, G.; J ibril, I. J . Chem. Soc., Dalton Trans.
1986, 377. (k) J ordan, R. F.; Bajgur, C. S.; Dasher, W. E.; Rheingold,
A. L. Organometallics 1987, 6, 1041. (l) Werner, H.; Knaup, W.;
Dziallas, M. Angew. Chem., Int. Ed. Engl. 1987, 26, 248. (m) Dormond,
A.; Aaliti, A.; Elbouadili, A.; Moise, C. J . Organomet. Chem. 1987, 329,
187. (n) Barron, A. R.; Salt, J . E.; Wilkinson, G.; Motevalli, M.;
Hursthouse, M. B. J . Chem. Soc., Dalton Trans. 1987, 2947. (o) Maatta,
E. A.; Du, Y. J . Am. Chem. Soc. 1988, 110, 8249. (p) Bochmann, M.;
Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988,
7, 1148. (q) Erker, G.; Fro¨mberg, W.; Kru¨ger, C.; Raabe, E. J . Am.
Chem. Soc. 1988, 110, 2400. (r) Colquhoun, H. M.; Crease, A. E.; Taylor,
S. A.; Williams, D. J . J . Chem. Soc., Dalton Trans. 1988, 2781. (s) Feng,
S. G.; Templeton, J . L. J . Am. Chem. Soc. 1989, 111, 6477. (t) Woo, H.
G.; Tilley, T. D. J . Organomet. Chem. 1990, 393, C6. (u) Borkowsky,
S. L.; J ordan, R. F.; Hinch, G. D. Organometallics 1991, 10, 1268. (v)
Daniel, T.; Mu¨ller, H.: Werner, H. Inorg. Chem. 1991, 30, 3118. (w)
Alelyunas, Y. W.; J ordan, R. F.; Echols, S. F.; Borkowsky, S. L.;
Bradley, P. K. Organometallics 1991, 10, 1406. (x) Feng, S. G.;
Templeton, J . L. Organometallics 1992, 11, 1295. (y) Debad, J . D.;
Legzdins, P.; Batchelor, R. J .; Einstein, F. W. B. Organometallics 1992,
11, 6.
(12) (a) Feng, S. G.; White, P. S.; Templeton, J . L. Organometallics
1993, 12, 1765. (b) Feng, S. G.; White, P. S.; Templeton, J . L.
Organometallics 1993, 12, 2131. (c) Werner, H.; Daniel, T.; Knaup,
W.; Nu¨rnberg, O. J . Organomet. Chem. 1993, 462, 309. (d) Daniel, T.;
Knaup, W.; Dziallas, M.; Werner, H. Chem. Ber. 1993, 126, 1981. (e)
Feng, S. G.; White, P. S.; Templeton, J . L. J . Am. Chem. Soc. 1994,
116, 8613. (f) Powell, K. R.; Pe´rez, P. J .; Luan, L.; Feng, S. G.; White,
P. S.; Brookhart, M.; Templeton, J . L. Organometallics 1994, 13, 1851.
(g) Daniel, T.; Werner, H. J . Chem. Soc., Dalton Trans. 1994, 221. (h)
Werner, H.; Daniel, T.; Braun, T.; Nu¨rnberg, O. J . Organomet. Chem.
1994, 480, 145. (i) Esteruelas, M. A.; Lahoz, F. J .; Oliva´n, M.; On˜ate,
E.; Oro, L. A. Organometallics 1994, 13, 3315. (j) Feng, S. G.; White,
P. S.; Templeton, J . L. Organometallics 1995, 14, 5184. (k) Francisco,
L. W.; White, P. S.; Templeton, J . L. Organometallics 1996, 15, 5127.
(l) Gunnoe, T. B.; White, P. S.; Templeton, J . L. J . Am. Chem. Soc.
1996, 118, 6916. (m) Werner, H.; Daniel, T.; Mu¨ller, M.; Mahr, N. J .
Organomet. Chem. 1996, 512, 197. (n) Cabeza, J . A.; del Rio, I.; Riera,
V. J . Organomet. Chem. 1997, 548, 255. (o) Cabeza, J . A.; del Rio, I.;
Franco, R. J .; Grepioni, F.; Riera, V. Organometallics 1997, 16, 2763.
(p) Cabeza, J . A.; del Rio, I.; Moreno, M.; Riera, V.; Grepioni, F.
Organometallics 1998, 17, 3027. (q) Cabeza, J . A.; del Rio, I.; Riera,
V.; Ardura, D. J . Organomet. Chem. 1998, 554, 117. (r) Bois, C.; Cabeza,
J . A.; Franco, R. J .; Riera, V.; Savorit, E. J . Organomet. Chem. 1998,
564, 201. (s) Schollhammer, P.; Pichon, M.; Muir, K. W.; Petillon, F.
Y.; Pichon, R.; Talarmin, J . Eur. J . Inorg. Chem. 1999, 221. (t) Brown,
S. N. Inorg. Chem. 2000, 39, 378. (u) J ime´nez-Tenorio, M. A.; J ime´nez-
Tenorio, M.; Puerta, M. C.; Valerga, P. Inorg. Chim. Acta 2000, 300,
869.
These hydride-azavinylidene complexes do not react
with phenylacetylene due to their saturated character.
However, the treatment of dichloromethane solutions
of OsHCl2(dNdCR2)(PiPr3)2 with Ag[CF3SO3] at room
temperature and the subsequent addition at -25 °C of
phenylacetylene affords the alkenyl derivatives [Os{(E)-
CHdCHPh}Cl(dNdCR2)(PiPr3)2]+. These compounds
(4) Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Martinez, M.-P.;
Oliva´n, M.; On˜ate, E.; Ruiz, N. Organometallics 1998, 17, 4500.
(5) 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, 4949.
(6) Buil, M. L.; Esteruelas, M. A.; Garc´ıa-Yebra, C.; Gutie´rrez-
Puebla, E.; Oliva´n, M. Organometallics 2000, 19, 2184.
(7) (a) Esteruelas, M. A.; Oro, L. A.; Valero, C. Organometallics 1995,
14, 3596. (b) Buil, M. L.; Esteruelas, M. A. Organometallics 2000, 18,
1798.
(8) Andriollo, A.; Esteruelas, M. A.; Meyer, U.; Oro, L. A.; Sa´nchez-
Delgado, R. A.; Sola, E.; Valero, C.; Werner, H. J . Am. Chem. Soc. 1989,
111, 7431.
(9) See for example: (a) Werner, H.; Esteruelas, M. A.; Otto, H.
Organometallics 1986, 5, 2295. (b) Werner, H.; Meyer, U.; Peters, K.;
von Schnering, H. G. Chem. Ber. 1989, 112, 2097. (c) Esteruelas, M.
A.; Lahoz, F. J .; Lo´pez, J . A.; Oro, L. A.; Schlu¨nken, C.; Valero, C.;
Werner, H. Organometallics 1992, 11, 2034.
(13) (a) Wade, R. C. In Catalysis of Organic Reactions; Moser, W.
R., Ed.; Marcel Dekker: New York, 1981. (b) Rhodes, L. F.; Venanzi,
L. M. Inorg. Chem. 1987, 26, 2692.
(14) Bohanna, C.; Esteruelas, M. A.; Lo´pez, A. M.; Oro, L. A. J .
Organomet. Chem. 1996, 526, 73.
(15) Daniel, T.; Werner, H. Z. Naturforsch., B 1992, 47, 1707.
(16) 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.
(17) Castarlenas, R.; Esteruelas, M. A.; On˜ate, E. Organometallics
2000, 19, 5454.
(10) (a) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Zeier,
B. Organometallics 1994, 13, 1662. (b) Esteruelas, M. A.; Lahoz, F. J .;
On˜ate, E.; Oro, L. A.; Zeier, B. Organometallics 1994, 13, 4258.

Azavinylidene-Carbyne Complexes of Os(II)
Organometallics, Vol. 20, No. 15, 2001 3285
carbyne, and show that not only the reaction products
from dihydrides and alkynes are the result of a sophis-
ticated combination of electronic factors involving the
metal and the alkyne but also those formed from
monohydrides and alkynes.
Resu lts a n d Discu ssion
1. Rea ction s of OsHCl2(dNdCMe2)(P iP r 3)2 w ith
HCtCR. Treatment at room temperature of dichloro-
methane solutions of OsHCl2(dNdCMe2)(PiPr3)2 (1)
with 1.0 equiv of Ag[CF3SO3], and the subsequent
stirring of the resulting solution under an acetylene
atmosphere, gives rise to the five-coordinate azavin-
ylidene-carbyne complex [OsCl(dNdCMe2)(tCCH3)-
(PiPr3)2][CF3SO3] (2). The related compounds [OsCl-
(dNdCMe2)(tCCH2R)(PiPr3)2][CF3SO3] (R ) Cy (3),
(CH2)2CH3 (4)) were similarly prepared by reaction of
1 with Ag[CF3SO3] and the corresponding alkyne (eq
1).
F igu r e 1. Molecular diagram for the cation of [OsCl-
(dNdCMe2)(tCCH3)(PiPr3)2][CF3SO3] (2). Thermal ellip-
soids are shown at 50% probability.
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for th e Com p lex
[OsCl(dNdCMe2)(tCCH3)(P iP r 3)2][CF 3SO3] (2)
Os(1)-Cl
2.401(3)
2.426(3)
2.434(3)
1.720(13)
Os(1)-N
1.871(8)
1.267(13)
1.488(19)
Os(1)-P(1)
Os(1)-P(2)
Os(1)-C(22)
N-C(19)
C(22)-C(23)
Cl-Os(1)-P(1)
Cl-Os(1)-P(2)
Cl-Os(1)-C(22)
Cl-Os(1)-N
P(1)-Os(1)-P(2)
P(1)-Os(1)-C(22)
87.25(11) P(1)-Os(1)-N
88.3(3)
97.9(4)
88.4(3)
111.6(5)
152.0(8)
169.4(12)
86.21(11) P(2)-Os(1)-C(22)
108.8(5)
139.6(3)
165.60(11) Os-N-C(19)
96.3(4)
P(2)-Os(1)-N
C(22)-Os(1)-N
Os-C(22)-C(23)
Complexes 2-4 were isolated as yellow solids in about
80% yield, and they were characterized by MS, elemen-
tal analysis, and IR and 31P{1H}, 1H, and 13C{1H} NMR
spectroscopy. Complex 2 was further characterized by
an X-ray crystallographic study. A view of the molecular
geometry of the cation of the complex is shown in Figure
1. Selected bond distances and angles are listed in Table
1.
The very short Os-C(22) bond length of 1.720(13) Å
is fully consistent with an Os-C(22) triple-bond formu-
lation. Similarly to other metal carbyne compounds,21
a slight bending in the Os-C(22)-C(23) moiety is also
present (Os-C(22)-C(23) ) 169.4(12)°).
The azavinylidene ligand coordinates to the osmium
atom in a bent fashion with an Os-N-C(19) angle of
152.0(8)°. A similar coordination mode has been ob-
served for the azavinylidene ligands of the osmium
The geometry around the osmium atom can be
rationalized as a distorted trigonal bipyramid with
apical phosphines (P(1)-Os-P(2) ) 165.60(11)°) and
inequivalent angles within the Y-shaped equatorial
plane. The angles C(22)-Os-N, C(22)-Os-Cl, and
N-Os-Cl are 111.6(5), 108.8(5), and 139.6(3)°, respec-
tively. This Y structure is similar to that found in the
vinylidene complex OsCl(dNdCMe2)(dCdCHPh)-
complexes
OsCl(dNdCMe2)(dCdCHPh)(PiPr3)2
(157.2(6)°),18 [Os{dNdC(Me)tBu}(η6-C6H6)(PiPr3)][PF6]
(167(2), 168(2), and 155(2)°),12m and cis-[OsCl2{dNd
C(Ph)(2-PhCOC6H4)}(terpy)][PF6] (168.3(3)°).12t The
Os-N distance of 1.871(8) Å is similar to that of OsCl-
(dNdCMe2)(dCdCHPh)(PiPr3)2 (1.873(5) Å)18 and in-
termediate between those found in OsCl2(dCdCHPh)-
(NHdCMe2)(PiPr3)2 (2.072(7) Å)17 and in the complexes
[Os{dNdC(Me)tBu}(η6-C6H6)(PiPr3)][PF6] (1.81(2) and
1.83(2)Å),12m and in cis-[OsCl2{dNdC(Ph)(2-PhCOC6H4)}-
(terpy)][PF6] (1.812(6) Å),12t while the N-C(19) distance
of 1.267(13) Å is similar to those found in the afore-
mentioned compounds.
(PiPr3)2 and the calculated structure for RuHCl(dCd
18
CH2)(PH3)2.19 However, it contrasts with the structure
of the carbene complexes RuCl2(dCR2)(PiPr3)2, in which
the carbene ligand occupies the apical position of a
square pyramid.20
(18) Castarlenas, R.; Esteruelas, M. A.; Gutie´rrez-Puebla, E.; On˜ate,
E. Organometallics 2001, 20, 1545.
(19) (a) 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.
In addition, it should be mentioned that the methyl
carbon atoms C(20) and C(21) form a plane with the
(21) Schubert, U. In Carbyne Complexes; Fischer, H., Hofmann, P.,
Kreissl, F. R., Schrock, R. R., Schubert, U., Weiss, K., Eds.; Verlags-
gesellschaft mbH: Weinheim, Germany, 1988; pp 40-58.

3286 Organometallics, Vol. 20, No. 15, 2001
Castarlenas et al.
Os-C-N unit, which is perpendicular to the best plane
containing the phosphorus atoms of the phosphine
ligands and the osmium atom (89.8(3)°).
served at about 270 ppm, as triplets with C-P coupling
constants of about 11 Hz and between 110 and 90 ppm
as singlets. The 31P{1H} NMR spectra contain singlets
at about 3 ppm.
2. Azavin yliden e-Alken yl an d Im in e-Vin yliden e
Sp ecies a s In ter m ed ia tes in th e F or m a tion of 2-4.
To obtain information about the formation of 2-4, we
have carried out at -25 °C the addition of cyclohexyl-
acetylene to the solution resulting from the treatment
of 1 with [AgCF3SO3]. Under these conditions the
alkenyl derivative [Os{(E)-CHdCHCy}Cl(dNdCMe2)-
(PiPr3)2][CF3SO3] (8) was obtained after 5 h, as a green
solid in 70% yield (eq 3).
The IR and 1H, 31P{1H}, and 13C{1H} NMR spectra
of 2-4 are consistent with the structure shown in
Figure 1. The IR spectra in KBr contain a ν(CdN) band
at about 1670 cm-1, along with the characteristic
stretching bands of the free [CF3SO3]- anion22 (see
Experimental Section), in agreement with the salt
character of the complexes. Because the azavinylidene
ligand lies in the Y plane, the methyl groups are
inequivalent and, in the 1H NMR spectrum, they display
two singlets between 2.6 and 2.2 ppm. The resonances
corresponding to the hydrogen atoms bonded to the Câ
atom of the carbyne groups are observed between 2.9
and 2.5 ppm. The 13C{1H} NMR spectra show the
characteristic OstC resonance of the carbyne ligands,
which appear at about 290 ppm as triplets with C-P
coupling constants of about 5 Hz. The 31P{1H} NMR
spectra contain singlets between 36 and 33 ppm.
Complexes 2-4 react with MeLi to give the azavin-
ylidene-vinylidene derivatives OsCl(dNdCMe2)(dCd
CHR)(PiPr3)2 (R ) H (5), Cy (6), (CH2)2CH3 (7)), as a
result of the extraction of a proton of the â-CH2 groups
(eq 2).
The unsaturated character of 8 is strongly supported
by its IR spectrum in KBr, which contains the charac-
teristic stretching bands of the free [CF3SO3]- anion at
1
1274, 1223, 1150, and 1032 cm-1. The H NMR spec-
trum in dichloromethane-d2 at -30 °C confirms the
presence of the alkenyl group with an E stereochemistry
and suggests that the Hâ atom interacts with the metal
to form an agostic bond. Thus, the resonance corre-
sponding to the vinylic HR atom is observed at 6.08 ppm,
in agreement with the chemical shift reported for Os-
{(E)-CHdCHCy}Cl(CO)(PiPr3)2 (6.80 ppm).7a However,
according to a 1H-1H COSY spectrum, the resonance
due to the Hâ atom lies at about 2.70 ppm, shifted about
2 ppm to higher field in comparison with that found in
the carbonyl complex (4.60 ppm), which does not show
agostic interaction. In agreement with the agostic
interaction the value of the HR-Hâ coupling constant
in 8 (9.5 Hz) is lower than that found in Os{(E)-CHd
CHCy}Cl(CO)(PiPr3)2 (12.6 Hz). The 13C NMR spectrum
is also consistent with a weak interaction between the
Hâ atom of the alkenyl ligand and the osmium atom.
The Câ resonance appears at 138.0 ppm with a C-H
coupling constant of 142.5 Hz, a significantly low value
Complexes 5 and 6 were obtained as orange solids in
73% and 80% yields, respectively, whereas complex 7
was obtained as an orange oil in quantitative yield. The
spectroscopic data of these complexes agree well with
those previously reported for the related compound
OsCl(dNdCMe2)(dCdCHPh)(PiPr3)2, where the trigo-
nal-bipyramidal geometry around the osmium atom and
the bent coordination of the azavinylidene have been
proved by an X-ray diffraction analysis.18 In agreement
with the presence of the azavinylidene and vinylidene
ligands, the IR spectra in KBr of the three compounds
show ν(CdN) and ν(OsdCdC) bands at about 1660 cm-1
and between 1625 and 1605 cm-1, respectively. As in
2-4 the azavinylidene ligand of 5-7 lies in the Y plane.
Thus, the 1H NMR spectra show two methyl resonances
between 2.2 and 1.9 ppm, corresponding to the in-
equivalent methyl groups of the azavinylidene. The
resonance due to the dCH hydrogen atom of the
vinylidene ligands appears between 1.6 and 2.3 ppm.
The 13C{1H} NMR spectra show the characteristic CR
and Câ resonances of the vinylidenes, which are ob-
1
compared to the J (C-H) value of 154.5 Hz correspond-
ing to the CR resonance, which is observed at 143.1 ppm.
The 31P{1H} NMR spectrum shows a singlet at -1.7
ppm. These spectroscopic data agree well with those
previously reported for the styryl complex [Os{(E)-CHd
CHPh}Cl(dNdCMe2)(PiPr3)2][CF3SO3], where the Hâ
atom of the styryl ligand also interacts with the metal.17
In solution at room temperature there is a marked
difference in behavior between the aforementioned
styryl compound and 8. While the former species evolves
into mixtures of five products, none of them are aza-
vinylidene-carbyne derivatives; complex 8 affords 3 as
(22) Lawrence, G. A. Chem. Rev. 1986, 86, 17.

Azavinylidene-Carbyne Complexes of Os(II)
Organometallics, Vol. 20, No. 15, 2001 3287
Sch em e 1
a consequence of a 1,2-hydrogen shift within the alkenyl
group. However, at -30 °C the behavior is not very
different. The addition of NaCl to tetrahydrofuran
solutions of 8 gives rise to the imine-vinylidene deriva-
tive OsCl2(dCdCHCy)(NHdCMe2)(PiPr3)2 (9), as a re-
sult of the hydrogen transfer from the alkenyl group to
the azavinylidene ligand (eq 4). Under the same condi-
Moreover, their protonation affords imine-carbyne
derivatives, which regenerate the imine-vinylidenes by
deprotonation. This suggests that for R ) Ph the imine-
vinylidene form is thermodynamically more stable than
the azavinylidene-carbyne form. The higher stability
of the imine-vinylidene form could be related to a
conjugating effect between the phenyl group and the
π-system of the vinylidene. A similar situation has been
previously observed between osmacyclopropene and
osmium carbyne species. While for R ) H and alkyl the
osmium carbyne form is thermodynamically more stable
than the cyclic one, there is a reversal in the relative
energy of the isomers for R ) Ph.5
tions, the styryl compound initially affords Os{(E)-CHd
CHPh}Cl2(dNdCMe2)(PiPr3)2, which evolves into the
corresponding imine-vinylidene at room temperature.
Complex 9 was isolated as an orange solid in 86%
yield. In agreement with the presence of the imine
ligand, the IR spectrum in KBr contains a ν(N-H) band
1
at 3201 cm-1. In the H NMR spectrum in toluene-d8
at -20 °C, the NH resonance appears at 11.33 ppm. The
3. Rea ction s of OsHCl2(dNdCMe2)(P iP r 3)2 w ith
2-Meth yl-1-bu ten -3-yn e. Treatment at room temper-
ature of dichloromethane solutions of 1 with 1.0 equiv
of Ag[CF3SO3] and the subsequent addition of 1.0 equiv
of 2-methyl-1-buten-3-yne leads after 4 h to the azavin-
ylidene-alkenylcarbyne derivative [OsHCl(dNdCMe2)-
(tC-CHdCMe2)(PiPr3)2][CF3SO3] (10), according to eq
5.
spectrum is in accordance with the mutually cis disposi-
i
tion of the chloride ligands, showing two Pr methyl
chemical shifts. In the 13C{1H} NMR spectrum, the
resonance due to the CR atom of the vinylidene is
observed at 287.6 ppm as a triplet with a C-P coupling
constant of 9.7 Hz, whereas the Câ atom displays a
singlet at 110.3 ppm. The 31P{1H} NMR spectrum shows
a singlet at -21.2 ppm.
In dichloromethane-d2, at room temperature, complex
9 dissociates a chloride and evolves into 3, as a result
of the hydrogen transfer from the imine to the Câ atom
of the vinylidene. After 24 h, the transformation is
quantitative. This reaction along with those showed in
eqs 3 and 4 suggest that the formation of 2-4, according
to eq 1, proceeds via the elemental steps summarized
in Scheme 1. The extraction of a chloride ligand from 1
activates the metallic center for the insertion of the
alkyne into the Os-H bond. The formed alkenyl ligand
evolves into a carbyne group by a double hydrogen
transfer reaction involving the azavinylidene ligand.
The first step of this formal 1,2-hydrogen shift takes
place between the CR atom of the alkenyl and the N
atom of the azavinylidene, whereas the second one
involves the N and Câ atoms of the resulting imine and
vinylidene ligands. The latter step is in agreement with
the expected electrophilic character of the hydrogen
atom of the imine and the well-known nucleophilic
nature of the Câ atoms of the vinylidene ligands.23
In contrast to 9, the imine-phenylvinylidene com-
plexes OsCl2(dCdCHPh)(NHdCR2)(PiPr3)2 do not evolve
into the corresponding azavinylidene-carbyne species.17
Complex 10 was isolated as a yellow solid in 77%
yield. In the H NMR spectrum in chloroform-d at room
1
temperature, the most noticeable resonances are those
corresponding to the alkenylcarbyne group, which ap-
pear as singlets at 6.07 (dCH) and 2.09 and 1.88 ppm
(CH3). As in 2-5, the methyl groups of the azavin-
ylidene display two resonances, indicating that the
(23) Kostic, N. M.; Fenske, R. F. Organometallics 1982, 1, 974.

3288 Organometallics, Vol. 20, No. 15, 2001
Castarlenas et al.
disposition of this ligand is as shown in Figure 1. The
13C{1H} NMR spectrum shows the resonance due to the
C(sp) atom of this ligand at 278.9 ppm, as a triplet with
a C-P coupling constant of 5.5 Hz, whereas those
corresponding to the C(sp2) atoms are observed as
singlets at 170.5 and 136.9 ppm. The 31P{1H} NMR
spectrum contains a singlet at 32.1 ppm.
Similarly to 2-4, complex 10 can be deprotonated by
MeLi. However, the deprotonation does not occur at the
Câ atom of the carbyne but at one of the two methyl
groups of the alkenyl unit. As a result, the treatment
at room temperature of tetrahydrofuran solutions of 10
with MeLi affords the novel azavinylidene-alkenyl-
vinylidene compound OsCl(dNdCMe2){dCdCHC(Me)d
CH2}(PiPr3)2 (11), according to eq 6.
whose molecular structure is formally regarded as the
result of either 1,2-addition of the Ru-H to the double
bond or 1,4-addition of the Ru-H to the conjugated
enyne.26
The structure proposed for 12 in eq 7 is consistent
1
with the IR and H, 13C, and 31P{1H} NMR spectra of
this compound. The IR in KBr contains the character-
istic stretching bands of the free [CF3SO3]- anion, at
1281, 1221, 1140, and 1031 cm-1, in agreement with the
1
salt nature of the compound. The H NMR spectrum,
in dichloromethane-d2 at -30 °C, suggest that the
OsCHdCHR unit has an E stereochemistry and that,
in a manner similar to 8, the Hâ atom interacts with
the metal to form an agostic bond. Thus, this resonance
appears at 3.73 ppm, shifted between 2 and 4 ppm to
higher field in comparison with those found in other
butadienyl compounds without agostic interactions.3,4,24,25
The value of the H-H coupling constant (10.5 Hz) is
similar to that found in 8 and between 3 and 8 Hz lower
than those observed in other (E)-butadienyl derivatives.
In the 13C NMR spectrum the resonances of the buta-
dienyl ligand appear at 145.2 (Câ), 141.5 (CR), 137.3 (Cγ),
and 115.9 (Cδ) ppm. In agreement with the Hâ-Os
Complex 11 was isolated as an orange microcrystal-
line solid in 73% yield. The presence of the alkenyl-
1
vinylidene ligand in 11 is strongly supported by the H
and 13C{1H} NMR spectra of this complex in dichlo-
romethane-d2, at room temperature. In the 1H NMR
spectrum, the unsaturated η1-carbon ligand gives rise
to three singlets at 4.56 and 4.08 ppm (dCH2) and 2.11
ppm (CH3) and a triplet at 3.27 ppm with a H-P
coupling constant of 3.3 Hz, which corresponds to the
â-CH proton. In the 13C{1H} NMR spectrum, the CR and
Câ resonances of the vinylidene unit appear at 275.2 and
116.6 ppm, the first of them as a triplet with a C-P
coupling constant of 10.5 Hz, whereas the second one
is observed as a singlet. The C(sp2) atoms of the alkenyl
unit display singlets at 137.9 and 100.6 ppm. The 31P-
{1H} NMR spectrum contains a singlet at 2.9 ppm.
To obtain information about the formation of 10, we
carried out at -25 °C the addition of 2-methyl-1-buten-
3-yne to the solution resulting from the treatment of 1
with Ag[CF3SO3]. Under these conditions the butadienyl
derivative [Os{(E)-CHdCHC(Me)dCH2}(dNdCMe2)-
(PiPr3)2][CF3SO3] (12) was obtained after 5 h as a green
solid in 74% yield (eq 7).
1
interaction, the J (Câ-H) value of 137.3 Hz is signifi-
1
cantly lower than the J (CR-H) and 1J (Cδ-H) values
of 154.1 and 158.5 Hz, respectively. The 31P{1H} NMR
spectrum contains a singlet at -0.6 ppm.
In solution at room temperature, complex 12 evolves
into 10, indicating that 12 is an intermediate in the
formation of 10, as 8 is intermediate in the formation
of 3. However, it should be noted that while the
formation of 3 involves a formal 1,2-hydrogen shift in
the alkenyl ligand of 8, the formation of 10 involves a
formal 1,4-hydrogen shift in the butadienyl ligand of 12.
This 1,4-hydrogen shift is the result of the hydrogen
transfer from the CR atom of the butadienyl ligand to
the nitrogen atom of the azavinylidene group and the
subsequent hydrogen transfer from the nitrogen atom
of the resulting imine to the Cδ atom of the resulting
alkenylvinylidene. In this context, it should be men-
tioned that the addition of H+ to the Cδ atom of
alkenylvinylidene ligands is a general method to pre-
pare alkenylcarbyne compounds.27
Complex 12 is the result of the extraction of a chloride
ligand from 1 and the selective addition of the Os-H
bond to the carbon-carbon triple bond of the enyne. A
similar addition has been previously observed for the
five-coordinate monohydrides MHCl(CO)(PiPr3)2 (M )
Ru,24 Os3) and RhH(SnPh3)(acac)(PCy3).25 In contrast,
the reaction of cis-(Me3Si)CHdCHCdCSiMe3 with the
six-coordinate RuHCl(CO)(PPh3)3 gives a stable complex
(24) Esteruelas, M. A.; Liu, F.; On˜ate, E.; Sola, E.; Zeier, B.
Organometallics 1997, 16, 2919.
(25) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E. Oro, L. A.; Rodriguez,
L. Organometallics 1996, 15, 3670.
(26) Wakatsuki, Y.; Yamazaki, H.; Maraguma, Y.; Shimizu, I. J .
Chem. Soc., Chem. Commun. 1991, 261.

Azavinylidene-Carbyne Complexes of Os(II)
Organometallics, Vol. 20, No. 15, 2001 3289
4. Rea ction s of OsHCl2(dNdCMe2)(P iP r 3)2 w ith
HCtCC(OH)P h R. Azavinylidene-alkenylcarbyne com-
plexes related to 10 can be also obtained from alkynols.
At room temperature, the addition of 1-phenyl-2-propyn-
1-ol, 2-phenyl-3-butyn-2-ol, and 1,1-diphenyl-2-propyn-
1-ol to the solutions resulting from the treatment of 1
with Ag[CF3SO3] leads to the complexes [OsCl(dNd
CMe2)(tCCHdCPhR)(PiPr3)2][CF3SO3] (R ) H (13),
CH3 (14), Ph (15)), according to eq 8. The formation of
deprotonation of the Câ atom of the alkenylcarbyne of
14 is not observed. In agreement with this, complexes
13 and 15 are inert in the presence of MeLi.
Complex 16 was isolated as an orange microcrystal-
1
line solid in 72% yield. The H, 13C{1H}, and 31P{1H}
NMR spectra of 16 agree well with that of 11. In the
1H NMR spectrum, the dCH resonance of the vinylidene
unit is observed at 3.23 ppm, as a triplet with a H-P
coupling constant of 3.0 Hz, whereas the dCH2 group
of the alkenyl unit displays two singlets at 5.40 and 5.19
ppm. In the 13C{1H} NMR spectrum, the CR and Câ
resonances of the vinylidene appear at 275.7 and 112.0
ppm, respectively, the first of them as a triplet with a
C-P coupling constant of 11.0 Hz, whereas the second
one is observed as a singlet. The vinyl carbon atoms of
the alkenyl unit display singlets at 131.9 and 105.4 ppm.
The 31P{1H} NMR spectrum shows a singlet at 4.6 ppm.
Con clu d in g Rem a r k s
This paper reveals the existence of two novel types
of difunctional organometallic compounds: the five-
coordinate azavinylidene-carbyne [OsCl(dNdCMe2)-
(tCCH2R)(PiPr3)2][CF3SO3] (R ) H, alkyl) and the five-
coordinate azavinylidene-alkenylcarbyne [OsCl(dNd
CMe2)(tCCHdCRR′)(PiPr3)2][CF3SO3] (R, R′ ) H, alkyl,
phenyl), which by deprotonation yield the corresponding
five-coordinate azavinylidene-vinylidene OsCl(dNd
CMe2)(dCdCHR)(PiPr3)2 and azavinylidene-alkenyl-
vinylidene OsCl(dNdCMe2){dCdCHC(R)dCH2}(PiPr3)2.
these compounds probably involves imine-hydroxy-
vinylidene intermediates related to 9, which evolves into
the corresponding carbyne derivatives by protonation
of the OH group with the N-H of the imine.
Complexes 13-15 were isolated as brown (13 and 15)
1
or light pink (14) solids in about 80% yield. In the H
The formation of the carbyne ligand of [OsCl(dNd
CMe2)(tCCH2R)(PiPr3)2][CF3SO3] is the result of the
extraction of a chloride from the complex OsHCl2(dNd
CMe2)(PiPr3)2 and the subsequent addition of the Os-H
bond to the alkynes HCtCR (R ) H, alkyl). The
reactions initially give azavinylidene-alkenyl interme-
diates, which evolve by a formal 1,2-hydrogen shift
within the alkenyl group into the carbynes. This hy-
drogen shift involves (i) the hydrogen transfer from the
CR atom of the alkenyl ligand to the nitrogen atom of
the azavinylidene group to afford imine-vinylidene
species and (ii) the NH hydrogen migration from the
imine to the Câ atom of the vinylidene.
NMR spectra, the most noticeable resonances are those
corresponding to the â-CH hydrogen atom of the carbyne
ligands, which appear at about 7 ppm. The 13C{1H}
NMR spectra agree well with that of 10. The resonances
due to the C(sp) atom of the unsaturated η1-carbon
ligands are observed at about 280 ppm, as triplets with
C-P coupling constants of about 6 Hz, whereas the
resonances corresponding to the C(sp2) atoms appears
at about 160 and 130 ppm as singlets. The 31P{1H} NMR
spectra show singlets between 28 and 34 ppm.
Similarly to 10, the addition of MeLi to tetrahydro-
furan solutions of 14 produces the deprotonation of the
methyl group of the alkenyl unit, to afford the aza-
vinylidene-alkenylvinylidene OsCl(dNdCMe2){dCd
CHC(Ph)dCH2}(PiPr3)2 (16), according to eq 9. The
Azavinylidene-alkenylcarbynes are similarly formed
from OsHCl2(dNdCMe2)(PiPr3)2 and enynes (HCtCC-
(Me)dCH2) or alkynols (HCtCC(OH)PhR). In this case
the reactions initially give azavinylidene-butadienyl or
azavinylidene-hydroxyvinylidene intermediates, which
evolve into imine-alkenylvinylidenes or imine-hydroxy-
vinylidenes, respectively. The imine-alkenylvinylidenes
afford azavinylidene-alkenylcarbynes by migration of
the NH hydrogen atom from the imine to the Cδ atom
of the alkenylvinylidene ligand, whereas the imine-
hydroxyvinylidenes afford azavinylidene-alkenylcar-
bynes by protonation of the OH group of the hydroxy-
vinylidene with the NH of the imine.
In conclusion azavinylidene-carbyne and azavin-
ylidene-alkenylcarbyne complexes can be prepared in
a one-pot synthesis by reaction of hydride-azavin-
ylidenes with terminal alkynes and enynes or alkynols,
respectively. The formation of these species takes place
via a novel hydrogen shift in the alkynes, which is
promoted by the azavinylidene ligand.
(27) Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa, J . I. Orga-
nometallics 1997, 16, 4657 and references therein.

3290 Organometallics, Vol. 20, No. 15, 2001
Castarlenas et al.
(CD2Cl2, 20 °C): δ 2.61 (t, J H-H ) 7.2, 2H, â-CH2); 2.39 (m,
6H, PCH); 2.22 (br, 6H, {CH3}2CdN); 1.70 (tt, J H-H ) 7.2, J H-H
) 6.9, 2H, γ-CH2); 1.29 (ct, J H-H ) 7.2, J H-H ) 6.9, 2H, δ-CH2);
1.07 and 1.05 (both dvt, J H-H ) 7.2, N ) 13.5, 36H, PCHCH3);
0.79 (t, J H-H ) 7.2, 3H, CH3). 13C{1H}-APT NMR (CD2Cl2, 20
°C): δ 295.3 (t, J C-P ) 5.2, OstC); 162.3 (t, J C-P ) 3.0, Osd
NdC); 121.4 (q, J C-F ) 321.2, CF3); 55.0, 27.3, and 22.0 (all s,
CH2); 25.4 and 22.2 (both s, {CH3}2CN); 23.4 (vt, N ) 26.7,
PCH); 19.8 and 19.4 (both s, PCHCH3); 17.7 (s, CH3). 31P{1H}
NMR (CD2Cl2, 20 °C): δ 33.9 (s). MS (FAB+): m/z 672 (M+).
P r ep a r a t ion of OsCl{dNdC(CH 3)2}(dCdCH 2)(P iP r 3)2
(5). A yellow solution of 2 in tetrahydrofuran (100 mg, 0.128
mmol) was treated with a solution of MeLi (80 µL, 1.6 M in
diethyl ether, 0.128 mmol) at room temperature. The color
changed immediately to orange and the solvent was concen-
trated to dryness. Then 8 mL of toluene was added to eliminate
by filtration the Li[CF3SO3] formed. After the toluene was
removed, addition of methanol yielded an orange microcrys-
talline solid that was washed twice with methanol and dried
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 material OsHCl2{dNdC(CH3)2}(PiPr3)2 (1) was pre-
pared 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.
P r ep a r a tion of [OsCl{dNdC(CH3)2}(tCCH3)(P iP r 3)2]-
[CF 3SO3] (2). A pale 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 resulting blue solution was
stirred under an acetylene atmosphere for 1 h. After the color
changed to yellow, the solvent was concentrated to ca. 0.5 mL.
Addition of diethyl ether yielded a yellow precipitate that was
washed with diethyl ether (3 × 2 mL) and dried in vacuo.
Yield: 90 mg (74%). Anal. Calcd for C24H51NSClF3O3OsP2: C,
37.03; H, 6.60; N, 1.79; S, 4.11. Found: C, 37.05; H, 6.21; N,
2.16; S, 3.91. IR (KBr, cm-1): ν(CdN) 1671 (m); νa(SO3) 1281
(s); νs(CF3) 1223 (s); νa(CF3) 1143 (s); νs(SO3) 1030 (s); δa(SO3)
in vacuo. Yield: 65 mg (80%). Anal. Calcd for
C23H50-
NClOsP2: C, 43.97; H, 8.02; N, 2.23. Found: C, 44.12; H, 7.92;
N, 2.11. IR (KBr, cm-1): ν(CdN) 1658 (m); ν(OsdCdC) 1607
(s). 1H NMR (C6D6, 20 °C): δ 2.76 (m, 6H, PCH); 2.19 and 1.93
(both s, 6H, {CH3}2CdN); 2.01 (t, J H-P ) 3.6, 2H, OsdCdCH2);
1.37 and 1.23 (both dvt, J H-H ) 6.6, N ) 13.5, 36H, PCHCH3).
13C{1H}-APT NMR (C6D6, 20 °C): δ 271.3 (t, J C-P ) 11.1, Osd
C); 152.6 (t, J C-P ) 3.2, CdN); 91.2 (s, OsdCdCH2); 23.0 and
21.0 (both t, J C-P ) 2.0, {CH3}2CdN); 22.8 (vt, N ) 28.5, PCH);
19.7 and 19.6 (both s, PCHCH3). 31P{1H} NMR (C6D6, 20 °C):
δ 3.6 (s). MS (FAB+): m/z 629 (M+).
1
638 (s). H NMR (CD2Cl2, 20 °C): δ 2.71 (m, 6H, PCH); 2.52
(s, 3H, OstCCH3); 2.43 and 2.34 (both t, J H-P ) 2.1, 6H,
{CH3}2CdN); 1.36 and 1.33 (both dvt, J H-H ) 7.2, N ) 13.5,
36H, PCHCH3). 13C{1H} NMR (CD2Cl2, 20 °C): δ 290.5 (t, J C-P
) 5.5, OstC); 162.1 (t, J C-P ) 3.6, OsdNdC); 121.4 (q, J C-F
) 321.2, CF3); 43.0 (s, OstCCH3); 25.3 and 22.2 (both s,
{CH3}2CdN); 24.2 (vt, N ) 26.2, PCH); 19.8 and 19.4 (both s,
PCHCH3). 31P{1H} NMR (CD2Cl2, 20 °C): δ 36.1 (s). MS
(FAB+): m/z 630 (M+).
P r ep a r a tion of[OsCl{dNdC(CH3)2}(tCCH2Cy)(P iP r 3)2]-
[CF 3SO3] (3). A pale 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. After 20 µL (0.157 mmol) of
cyclohexylacetylene was added, the reaction mixture was
stirred for 1 h at room temperature. The color changed to
yellow, and the solvent was concentrated to ca. 0.5 mL.
Addition of diethyl ether yielded a yellow precipitate that was
washed with diethyl ether (3 × 2 mL) and dried in vacuo.
Yield: 105 mg (77%). Anal. Calcd for C30H61NSClF3O3OsP2:
C, 41.88; H, 7.15; N, 1.63; S, 3.73. Found: C, 42.03; H, 7.31;
N, 1.73; S, 3.68. IR (KBr, cm-1): ν(CdN) 1670 (m); νa(SO3)
1263 (s); νs(CF3) 1223 (s); νa(CF3) 1152 (s); νs(SO3) 1032 (s);
P r ep a r a tion of OsCl{dNdC(CH3)2}(dCdCHCy)(P iP r 3)2
(6). This complex was prepared as described for 5, starting
from 3 (100 mg, 0.116 mmol) and MeLi (75 µL, 1.6 M in diethyl
ether, 0.120 mmol). An orange solid was obtained. Yield: 60
mg (73%). Anal. Calcd for C29H60NClOsP2: C, 49.03; H, 8.51;
N, 1.97. Found: C, 48.65; H, 8.74; N, 1.99. IR (KBr, cm-1):
ν(CdN) 1655 (m); ν(OsdCdC) 1621 (s). 1H NMR (C6D6, 20
°C): δ 2.81 (m, 6H, PCH); 2.22 and 1.95 (both s, 6H, {CH3}2Cd
N); 2.02 (m, 4H, Cy); 1.80 (m, 4H, Cy); 1.64 (m, 1H, OsdCd
CHCy); 1.4-1.1 (m, 3H, Cy); 1.40 and 1.23 (both dvt, J H-H
)
6.9 Hz, N ) 13.2, 36H, PCHCH3). 13C{1H}-APT NMR (C6D6,
20 °C): δ 267.8 (t, J C-P ) 11.4, OsdC); 152.6 (t, J C-P ) 3.2,
CdN); 113.9 (s, OsdCdCHCy); 37.6, 27.0, and 26.6 (all s, CH2
Cy); 32.7 (s, CH Cy); 22.8 and 20.7 (both s, {CH3}2CdN); 22.3
(vt, N ) 23.0, PCH); 19.6 and 19.4 (both s, PCHCH3). 31P{1H}
NMR (C6D6, 20 °C): δ 2.8 (s). MS (FAB+): m/z 711 (M+).
P r epar ation of OsCl{dNdC(CH3)2}{dCdCH(CH2)2CH3}-
(P iP r 3)2 (7). This complex was prepared as described for 5,
starting from 4 (100 mg, 0.122 mmol) and MeLi (77 µL, 1.6 M
in diethyl ether, 0.123 mmol). An orange oil was obtained. IR
(Nujol, cm-1): ν(CdN) 1659 (m); ν(OsdCdC) 1610 (s). 1H NMR
(C6D6, 20 °C): δ 2.76 (m, 8H, PCH and γ-CH2); 2.23 (t, J H-P
)
1
δa(SO3) 636 (s). H NMR (CD2Cl2, 20 °C): δ 2.95 (m, 2H, Ost
2.0, OsdCdCH); 2.20 and 1.96 (both s, 6H, {CH3}2CdN); 1.48
(ct, J H-H ) 7.2, J H-H ) 7.0, 2H, δ-CH2), 1.38 and 1.23 (both
dvt, J H-H ) 6.9, N ) 12.6, 36H, PCHCH3); 0.99 (t, J H-H ) 7.2,
CCH2); 2.89 (m, 6H, PCH); 2.60 and 2.48 (both t, J H-P ) 2.1,
6H, {CH3}2CdN); 2.19 (m, 1H, CH Cy); 2.0-1.2 (m, 10H, CH2
Cy); 1.52 and 1.48 (both dvt, J H-H ) 6.9, N ) 13.5, 36H,
3H, CH3). 13C{1H}-APT NMR (C6D6, 20 °C): δ 268.5 (t, J C-P
)
PCHCH3). 13C{1H} NMR (CD2Cl2, 20 °C): δ 295.2 (t, J C-P
5.5, OstC); 162.7 (t, J C-P ) 3.7, OsdNdC); 120.6 (q, J C-F
)
)
12.0, OsdC); 152.5 (t, J C-P ) 3.2, CdN); 106.7 (s, OsdCdC);
26.1 and 24.7 (both s, CH2); 22.0 and 20.8 (both s, {CH3}2Cd
N); 22.5 (vt, N ) 23.1, PCH); 19.6 and 19.5 (both s, PCHCH3);
14.1 (s, CH3). 31P{1H} NMR (C6D6, 20 °C): δ 2.9 (s). MS
(FAB+): m/z 671 (M+).
P r ep a r a t ion of [Os{(E)-CHdCHCy}Cl{dNdC(CH3)2}-
(P iP r 3)2][CF 3SO3] (8). A pale 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 30 µL (0.235 mmol) of cyclohexyl-
acetylene was added. The reaction mixture 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,
319.3, CF3); 63.1 (s, OstCCH2); 37.2, 26.2, and 25.8 (all s, CH2
Cy); 34.0 (s, CH Cy); 25.5 and 22.4 (both s, {CH3}2CdN); 24.1
(vt, N ) 26.1, PCH); 19.7 and 19.3 (both s, PCHCH3). 31P{1H}
NMR (CD2Cl2, 20 °C): δ 34.2 (s). MS (FAB+): m/z 712 (M+).
P r ep a r a t ion of [OsCl{dNdC(CH 3)2}{tC(CH 2)3CH 3}-
(P iP r 3)2][CF 3SO3] (4). This complex was prepared as de-
scribed for 3, starting from 1 (100 mg, 0.157 mmol), 40 mg
(0.157 mmol) of Ag[CF3SO3], and 16 µL (0.158 mmol) of
1-pentyne. A yellow solid was obtained. Yield: 110 mg (85%).
Anal. Calcd for C27H57NSClF3O3OsP2: C, 39.52; H, 7.00; N,
1.70; S, 3.90. Found: C, 39.55; H, 7.03; N, 1.83; S, 3.83. IR
(KBr, cm-1): ν(CdN) 1676 (m); νa(SO3) 1264 (s); νs(CF3) 1223
(s); νa(CF3) 1152 (s); νs(SO3) 1032 (s); δa(SO3) 637 (s). 1H NMR

Azavinylidene-Carbyne Complexes of Os(II)
Organometallics, Vol. 20, No. 15, 2001 3291
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 (70%). Anal. Calcd for C30H61NSClF3O3OsP2: C,
41.88; H, 7.15; N, 1.63; S, 3.73. Found: C, 41.65; H, 7.10; N,
1.72; S, 3.62. IR (KBr, cm-1): ν(CdN) 1671 (m); νa(SO3) 1274
(s); νs(CF3) 1223 (s); νa(CF3) 1150 (s); νs(SO3) 1032 (s); δa(SO3)
C, 46.73; H, 8.14; N, 2.10. Found: C, 46.52; H, 7.98; N, 2.07.
IR (KBr, cm-1): ν(CdN) 1671 (m); ν(OsdCdC) 1600 (s). 1H
NMR (C6D6, 20 °C): δ 4.56 and 4.08 (both s, 2H, dCH2); 3.27
(t, J H-P ) 3.3, 1H, OsdCdCH); 2.75 (m, 6H, PCH); 2.16 and
1.94 (both s, 6H, {CH3}2CdN); 2.11 (s, 3H, C{CH3}d); 1.34
and 1.18 (both dvt, J H-H ) 6.9, N ) 13.5, 36H, PCHCH3). 13C-
{1H} NMR (C6D6, 20 °C): δ 275.2 (t, J C-P ) 10.5, OsdC); 153.8
(s, CdN); 137.9 (s, C{CH3}d); 116.6 (s, OsdCdC); 100.6 (s,
dCH2); 30.2 (s, C{CH3}d); 23.1 (vt, N ) 23.0, PCH); 22.3 and
20.6 (both s, {CH3}2CdN); 19.9 and 19.6 (both s, PCHCH3).
31P{1H} NMR (C6D6, 20 °C): δ 2.9 (s). MS (FAB+): m/z 670
(M+ - H).
1
637 (s). H NMR (CD2Cl2, -30 °C): δ 6.08 (d, J H-H ) 9.5 Hz,
1H, Os-CHdCHCy); 3.89 and 3.68 (both s, 6H, {CH3}2CdN);
2.70 (m, 7H, PCH and Os-CHdCHCy); 1.7-1.2 (m, 11H, Cy);
1.32 and 1.24 (both dvt, J H-H ) 7.0, N ) 13.7, 36H, PCHCH3).
13C{1H} NMR (CD2Cl2, -30 °C): δ 160.0 (s, OsdNdC); 143.1
(s {d, J C-H ) 154.5 in 13C NMR (CD2Cl2, -30 °C)}, Os-CHd
CHCy); 138.0 (s {d, J C-H ) 142.5 in 13C NMR (CD2Cl2, -30
°C)}, Os-CHdCHCy); 120.6 (q, J C-F ) 318.7, CF3); 42.8, 26.3,
and 25.8 (all s, CH2 Cy); 35.1 (s, CH Cy); 22.8 (vt, N ) 23.0,
PCH); 19.2 and 19.0 (both s, PCHCH3); 10.1 and 7.8 (both s,
{CH3}2CdN). 31P{1H} NMR (CD2Cl2, -30 °C): δ -1.7 (s). MS
(FAB+): m/z 712 (M+).
P r ep a r a tion of [Os{(E)-CHdCHC(CH3)dCH2}Cl{dNd
C(CH3)2}(P iP r 3)2][CF 3SO3] (12). This complex was prepared
as described for 8, starting from 1 (100 mg, 0.157 mmol), 40
mg (0.157 mmol) of Ag[CF3SO3], and 15 µL (0.158 mmol) of
2-methyl-1-buten-3-yne. A green solid was obtained. Yield: 95
mg (74%). Anal. Calcd for C27H55NSClF3O3OsP2: C, 39.63; H,
6.77; N, 1.71; S, 3.91. Found: C, 39.53; H, 6.42; N, 1.67; S,
3.81. IR (KBr, cm-1): ν(CdN) 1648 (m); νa(SO3) 1281 (s); νs-
(CF3) 1221 (s); νa(CF3) 1140 (s); νs(SO3) 1031 (s); δa(SO3) 637
(s). 1H NMR (CD2Cl2, -30 °C): δ 7.25 (d, J H-H ) 10.5, 1H,
Os-CHdCH); 4.05 and 4.00 (both s, 2H, dCH2); 3.8 (br, 6H,
{CH3}2CdN); 3.73 (dt, J H-H ) 10.5, J H-P ) 4.5, 1H, Os-CHd
CH); 2.8 (m, 6H, PCH); 1.55 (s, 3H, C{CH3}d); 1.36 and 1.34
(both dvt, J H-H ) 7.5, N ) 14.1, 36H, PCHCH3). 13C{1H}-APT
NMR (CD2Cl2, -30 °C): δ 160.4 (s, OsdNdC); 145.2 (s, {d,
J C-H ) 137.3 in 13C NMR (CD2Cl2, -30 °C)}, Os-CHdCH);
141.5 (s, {d, J C-H ) 154.1 in 13C NMR (CD2Cl2, -30 °C)}, Os-
CHdCH); 137.3 (s, {t, J C-H ) 158.5 in 13C NMR (CD2Cl2, -30
°C)}, C{CH3}d); 120.6 (q, J C-F ) 318.7, CF3); 115.9 (s, dCH2);
22.8 (br, PCH); 22.6 (s, C{CH3}d); 19.2 and 19.0 (both s,
PCHCH3); 10.1 and 7.8 (both s, {CH3}2CdN). 31P{1H} NMR
(CD2Cl2, -30 °C): δ -0.6 (s). MS (FAB+): m/z 670 (M+).
P r ep a r a tion of [OsCl{dNdC(CH3)2}(tCCHdCHP h )-
(P iP r 3)2][CF 3SO3] (13). This complex was prepared as de-
scribed for 3, starting from 1 (100 mg, 0.157 mmol), 40 mg
(0.157 mmol) of Ag[CF3SO3], and 21 mg (0.158 mmol) of
1-phenyl-2-propyn-1-ol. A brown solid was obtained. Yield: 110
mg (80%). Anal. Calcd for C31H55NSClF3O3OsP2: C, 42.97; H,
6.39; N, 1.61; S, 3.69. Found: C, 42.72; H, 6.18; N, 1.79; S,
3.69. IR (KBr, cm-1): ν(CdN) 1670 (m); νa(SO3) 1275 (s); νs-
(CF3) 1223 (s); νa(CF3) 1148 (s); νs(SO3) 1036 (s); δa(SO3) 637
(s). 1H NMR (CDCl3, 20 °C): δ 7.75 (d, J H-H ) 7.5, 2H,
P r epar ation of OsCl2(dCdCHCy){NHdC(CH3)2}(P iP r 3)2
(9). A green solution of 8 (100 mg, 0.116 mmol) at -30 °C in
tetrahydrofuran was treated with NaCl (25 mg, 0.428 mmol)
and was kept stirring during 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 Na[CF3SO3] formed and the excess
NaCl. After the toluene was removed again at -30 °C, addition
of pentane at -50 °C yielded an orange precipitate that was
washed three times with cold pentane and dried in vacuo.
Yield: 75 mg (86%). Anal. Calcd for C29H61NCl2OsP2: C, 46.64;
H, 8.23; N, 1.88. Found: C, 46.58; H, 8.08; N, 1.70. IR (KBr,
cm-1): ν(N-H) 3201 (m); ν(CdN) 1656 (m); ν(OsdCdC) 1609
1
(s). H NMR (toluene-d8, -20 °C): δ 11.33 (s, 1H, N-H); 2.93
(m, 6H, PCH); 2.7-1.0 (m, 12H, OsdCdCHCy and Cy); 1.60
and 1.53 (both s, 6H, {CH3}2CdN); 1.33 (m, 36H, PCHCH3).
13C{1H} NMR (toluene-d8, -20 °C): δ 287.6 (t, J C-P ) 9.7, Osd
C); 173.6 (s, CdN); 110.3 (s, OsdCdC); 47.8, 24.8, and 24.3
(all s, CH2 Cy); 36.0 (s, CH Cy); 27.8 and 22.2 (both s,
{CH3}2CdN); 21.3 (br, PCH); 17.8 (br, PCHCH3). 31P{1H} NMR
(toluene-d8, -20 °C): δ -21.2 (s). MS (FAB+): m/z 712 (M+
Cl).
-
P r ep a r a tion of [OsCl{dNdC(CH3)2}{tCCHdC(CH3)2}-
(P iP r 3)2][CF 3SO3] (10). This complex was prepared as de-
scribed for 3, starting from 1 (100 mg, 0.157 mmol), 40 mg
(0.157 mmol) of Ag[CF3SO3], and 15 µL (0.158 mmol) of
2-methyl-1-buten-3-yne. A orange solid was obtained. Yield:
100 mg (77%). Anal. Calcd for C27H55NSClF3O3OsP2: C, 39.63;
H, 6.77; N, 1.71; S, 3.91. Found: C, 39.56; H, 6.50; N, 1.82; S,
3.96. IR (KBr, cm-1): ν(CdN) 1673 (m); νa(SO3) 1270 (s); νs-
(CF3) 1221 (s); νa(CF3) 1144 (s); νs(SO3) 1031 (s); δa(SO3) 636
(s). 1H NMR (CDCl3, 20 °C): δ 6.07 (s, 1H, CHd); 2.69 (m,
6H, PCH); 2.47 and 2.37 (both t, J H-P ) 2.0, 6H, {CH3}2Cd
N); 2.09 and 1.88 (both s, 6H, dC{CH3}2); 1.32 and 1.30 (both
dvt, J H-H ) 7.2, N ) 13.5, 36H, PCHCH3). 13C{1H}-APT NMR
(CDCl3, 20 °C): δ 278.9 (t, J C-P ) 5.5, OstC); 170.5 (s,
dC{CH3}2); 162.0 (t, J C-P ) 3.0, OsdNdC); 136.9 (s, CHd);
121.4 (q, J C-F ) 322.8, CF3); 26.6 and 24.6 (both s, dC{CH3}2);
24.8 and 22.0 (both t, J C-P ) 1.8, {CH3}2CdN); 23.7 (vt, N )
26.7, PCH); 19.6 and 19.2 (both s, PCHCH3). 31P{1H} NMR
(CDCl3, 20 °C): δ 32.1 (s). MS (FAB+): m/z 670 (M+).
P r ep a r a tion of OsCl{dNdC(CH3)2}{dCdCHC(CH3)d
CH2}(P iP r 3)2 (11). A orange solution of 10 in tetrahydrofuran
(100 mg, 0.122 mmol) was treated with a solution of MeLi (77
µL, 1.6 M in diethyl ether, 0.123 mmol) at room temperature.
After 5 min of reaction the solvent was concentrated to
dryness. Then 8 mL of toluene was added to eliminate by
filtration the Li[CF3SO3] formed. After the toluene was
removed, addition of 2 mL of methanol at -78 °C yielded an
orange microcrystalline solid that was washed with cold
methanol (2 × 1 mL) and pentane (3 × 2 mL) and dried in
vacuo. Yield: 60 mg (73%). Anal. Calcd for C26H54NClOsP2:
H
ortho-Ph); 7.73 (d, J H-H ) 15.8, 1H, CHdCHPh); 7.59 (t, J H-H
) 7.8, 1H, Hpara-Ph); 7.45 (t, J H-H ) 7.8, 2H, Hmeta-Ph); 7.12 (d,
J H-H ) 15.8, 1H, CHdCHPh); 2.71 (m, 6H, PCH); 2.53 and
2.50 (both t, J H-P ) 2.0, 6H, {CH3}2CdN); 1.36 and 1.33 (both
dvt, J H-H ) 7.2, N ) 14.1, 36H, PCHCH3). 13C{1H}-APT NMR
(CDCl3, 20 °C): δ 278.9 (t, J C-P ) 6.4, OstC); 162.4 (t, J C-P
)
3.6, OsdNdC); 151.7 (s, ) CHPh); 135.8, 130.2, and 129.5 (all
s, Ph); 133.6 (s, CHd); 133.0 (s, Cipso-Ph); 121.6 (q, J C-F ) 322.1,
CF3); 25.2 and 21.8 (both s, {CH3}2CdN); 24.2 (vt, N ) 25.5,
PCH); 19.8 and 19.5 (both s, PCHCH3). 31P{1H} NMR (CDCl3,
20 °C): δ 28.6 (s). MS (FAB+): m/z 718 (M+).
P r ep a r a tion of [OsCl{dNdC(CH3)2}{tCCHdC(CH3)-
P h }(P iP r 3)2][CF 3SO3] (14). This complex was prepared as
described for 3, starting from 1 (100 mg, 0.157 mmol), 40 mg
(0.157 mmol) of Ag[CF3SO3], and 23 mg (0.158 mmol) of
2-phenyl-3-butyn-2-ol. A light pink solid was obtained. Yield:
110 mg (79%). Anal. Calcd for C32H57NSClF3O3OsP2: C, 43.65;
H, 6.53; N, 1.59; S, 3.64. Found: C, 43.65; H, 6.86; N, 1.60; S,
3.64. IR (KBr, cm-1): ν(CdN) 1670 (m); νa(SO3) 1272 (s); νs-
(CF3) 1224 (s); νa(CF3) 1147 (s); νs(SO3) 1031 (s); δa(SO3) 637
(s). 1H NMR (CDCl3, 20 °C): δ 7.71 (d, J H-H ) 7.8, 2H,
H
ortho-Ph); 7.58 (t, J H-H ) 6.9, 1H, Hpara-Ph); 7.47 (t, J H-H )
7.8, 2H, Hmeta-Ph); 6.60 (s, 1H, CHd); 2.71 (m, 6H, PCH); 2.47
(br, {CH3}2CdN); 2.42 (s, 3H, dC{CH3}Ph); 1.33 and 1.29 (both
dvt, J H-H ) 7.2, N ) 14.1, 36H, PCHCH3). 13C{1H}-APT NMR
(CDCl3, 20 °C): δ 277.6 (t, J C-P ) 5.6, OstC); 162.5 (t, J C-P
)
3.2, OsdNdC); 162.4 (s, dC{CH3}Ph); 137.6 (s, Cipso-Ph); 134.6,

3292 Organometallics, Vol. 20, No. 15, 2001
Castarlenas et al.
Ta ble 2. Cr ysta l Da ta a n d Da ta Collection a n d
Refin em en t Deta ils for th e Com p lex
130.0, and 126.8 (all s, Ph); 132.8 (s, CHd); 121.6 (q, J C-F
)
320.1, CF3); 25.2 and 21.9 (both s, {CH3}2CdN); 23.8 (vt, N )
25.8, PCH); 21.2 (s, dC{CH3}Ph); 19.7 and 19.2 (both s,
PCHCH3). 31P{1H} NMR (CDCl3, 20 °C): δ 28.6 (s). MS
(FAB+): m/z 732 (M+).
[OsCl(dNdCMe2)(tCCH3)(P iP r 3)2][CF 3SO3] (2)
Crystal Data
formula
mol wt
C24H51ClF3NO3OsP2S
778.31
P r ep a r a tion of [OsCl{dNdC(CH3)2}{tCCHdC(P h )2}-
(P iP r 3)2][CF 3SO3] (15). This complex was prepared as de-
scribed for 3, starting from 1 (100 mg, 0.157 mmol), 40 mg
(0.157 mmol) of Ag[CF3SO3], and 33 mg (0.158 mmol) of 1,1-
diphenyl-2-propyn-1-ol. A brown solid was obtained. Yield: 115
mg (77%). Anal. Calcd for C37H59NSClF3O3OsP2: C, 47.15; H,
6.31; N, 1.49; S, 3.40. Found: C, 46.87; H, 6.45; N, 1.52; S,
3.49. IR (KBr, cm-1): ν(CdN) 1676 (m); νa(SO3) 1271 (s); νs-
(CF3) 1222 (s); νa(CF3) 1147 (s); νs(SO3) 1031 (s); δa(SO3) 636
(s). 1H NMR (acetone-d6, 20 °C): δ 7.7-7.4 (m, 10H, Ph); 6.86
(s, 1H, CHd); 2.86 (m, 6H, PCH); 2.65 (br, 6H, {CH3}2CdN);
1.36 and 1.32 (both dvt, J H-H ) 7.5, N ) 14.5, 36H, PCHCH3).
habit
irregular block
monoclinic, P21/n
13.146(1), 8.978(1), 28.245(4)
90, 94.28(1), 90
3324.3(7), 4
space group
a, b, c, Å
R, â, γ, deg
V, Å3; Z
D
calcd, g cm-3
1.555
Data Collection and Refinement Details
diffractometer
λ(Mo KR), Å
monochromator
µ, mm-1
Bruker-Siemens P4
0.710 73
graphite oriented
4.116
scan type
w
13C{1H} plus APT NMR (acetone-d6, 20 °C): δ 281.4 (t, J C-P
)
2θ range, deg
temp, K
3 e 2θ e 50
200.0(2)
6.0, OstC); 164.2 (t, J C-P ) 3.6, OsdNdC); 162.2 (s, dC{Ph}2);
140.5 and 139.0 (both s, Cipso-Ph); 136.3 (s, CHd); 136.0, 132.5,
132.3, 130.5, and 130.1 (all s, Ph); 121.6 (q, J C-F ) 322.1, CF3);
24.9 and 21.2 (both s, {CH3}2CdN); 23.8 (vt, N ) 22.5, PCH);
19.9 and 19.4 (both s, PCHCH3). 31P{1H} NMR (acetone-d6,
20 °C): δ 33.9 (s). MS (FAB+): m/z 794 (M+).
P r ep a r a t ion of OsCl{dNdC(CH 3)2}{dCdCH C(P h )d
CH2}(P iP r 3)2 (16). This complex was prepared as described
for 11, starting from 14 (100 mg, 0.113 mmol) and MeLi (72
µL, 1.6 M in diethyl ether, 0.115 mmol). An orange solid was
no. of data collect
hkl limits
no. of unique data
6385
0 to 15, -10 to +2, -33 to +33
5776 (merging R factor 0.0449)
no. of params refined/restraints 478/359
R1(F2> 2σ(F2))a
wR2(all data)b
S(all data)c
0.0615
0.1655
1.025
R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) {∑[w(Fo - Fc2)2]/
a
b
2
∑[w(Fo2)2]}1/2
.
c GOF ) S ) {∑[w(Fo - Fc2)2]/(n - p)}1/2, where n
2
is the number of reflections and p is the number of refined
obtained. Yield: 60 mg (72%). Anal. Calcd for
C31H56-
parameters.
NClOsP2: C, 50.98; H, 7.73; N, 1.92. Found: C, 50.80; H, 7.72;
N, 1.79. IR (KBr, cm-1): ν(CdN) 1676 (m); ν(OsdCdC) 1603
(s). 1H NMR (C6D6, 20 °C): δ 7.71 (d, J H-H ) 7.5, 2H, Hortho-Ph);
7.21 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 7.11 (t, J H-H ) 7.2, 1H,
and the triflate anion were observed to be severely disordered.
The triisopropylphosphine group was refined as two moieties
with complementary occupancy factors, with the same free
geometry, and isotropic thermal parameters. The triflate anion
was refined with common sulfur and carbon atoms but with
two moieties for each of the fluorine and oxygen atoms. The
complementary occupancy factors were restrained to amount
to 1; isotropic thermal parameters and restrained geometry
were also used. The rest of the non-hydrogen atoms were
anisotropically refined, and the hydrogen atoms of nondisor-
dered groups were observed or included at idealized positions.
Hpara-Ph); 5.40 and 5.19 (both s, 2H, dCH2); 3.23 (t, J H-P
)
3.0, 1H, OsdCdCH); 2.77 (m, 6H, PCH); 2.16 and 1.93 (both
s, 6H, {CH3}2CdN); 1.35 and 1.20 (both dvt, J H-H ) 6.9, N )
13.5, 36H, PCHCH3). 13C{1H} NMR (C6D6, 20 °C): δ 275.7 (t,
J C-P ) 11.0, OsdC); 153.8 (s, CdN); 145.2 (s, Cipso-Ph); 139.1
(s, C{Ph}d); 127.6, 126.9, and 126.6 (all s, CPh); 112.0 (s, Osd
CdC); 105.4 (s, dCH2); 22.8 (vt, N ) 23.0, PCH); 22.3 and 20.6
(both s, {CH3}2CdN); 19.7 and 19.4 (both s, PCHCH3). 31P-
{1H} NMR (C6D6, 20 °C): δ 4.6 (s). MS (FAB+): m/z 732 (M+
- H).
X-r a y Str u ctu r e An a lysis of Com p lex 2. Crystals suit-
able for X-ray diffraction analysis were mounted onto a glass
fiber and transferred to an Bruker-Siemens P4 automatic
diffractometer (200 K, Mo KR radiation, graphite monochro-
mator, λ ) 0.710 73 Å). A summary of crystal data and
refinement parameters is reported in Table 2. Accurate unit
cell parameters were determined by least-squares fitting from
the setting of high-angle reflections. Data were collected by
the ω scan method. Lorentz and polarization corrections were
applied. Decay was monitored by measuring three standards
throughout data collection. Corrections for decay and absorp-
tion (semiempirical ψ-scan method) were applied.
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 2. This
material is available free of charge via the Internet at
http://pubs.acs.org.
OM0101386
The structure was solved by Patterson methods and refined
(28) Sheldrick, G. M. University of Go¨ttingen, Go¨ttingen, Germany,
1997.
by full-matrix least squares on F2.28 A phosphine ligand (P(1))