Δ2- and Δ3-azaosmetine complexes as intermediates in the stoichiometric imination of phenylacetylene with oximes

Article abstract of DOI:10.1021/om010005k

Complexes [Os{(E)-CH=CHPh}Cl(=N=CR₂)(PⁱPr₃)₂] [CF₃SO₃] [CR₂ = CMe₂ (1), C(CH₂)₄CH₂ (2)] react with carbon monoxide to give the Δ²-1,2-azaosmetine derivatives [OsCl(=CHCH(Ph)N=CR₂)(CO)(PⁱPr₃)₂] [CF₃SO₃] [CR₂ = CMe₂ (3), C(CH₂)₄CH₂ (4)], as a result of the coordination of carbon monoxide to the osmium atoms of 1 and 2 and the carbon-nitrogen coupling between the styryl and azavinylidene ligands. The structure of 3 in the solid state has been determined by an X-ray diffraction study. Complexes 3 and 4 can be deprotonated with MeLi to give the Δ³-1,2-azaosmetine compounds Os{CH=C(Ph) N=CR₂}Cl(CO) (PⁱPr₃)₂ [CR₂ = CMe₂(5), C(CH₂)₄ CH₂ (6)], which react with molecular hydrogen to afford the 2-aza-1,3-butadienes CH₂=C(Ph)N=CR₂[CR₂ =CMe₂ (7), C(CH₂)₄CH₂ (8)] and OsH₂(η²-H₂)(CO)(PⁱPr₃ )₂. The carbonylation of the cations of 3 and 4 leads to [Os{(Z)-CH=C(Ph)NH=CR₂}Cl(CO)₂(PⁱPr₃ )₂]⁺ [CR₂ = CMe₂ (9), C(CH₂)₄CH₂ (10)]. The [BF₄]^- salts of 9 and 10 have been obtained by carbonylation of 5 and 6 and subsequent protonation of the resulting η¹-azabutadiene intermediates Os{(Z)-CH=C(Ph)N=CR₂}Cl(CO)₂(Pⁱ Pr₃)₂ [CR₂ = CMe₂ (11), C(CH₂)₄CH₂ (12)]. The structure of the [BF₄]^- salt of 10 in the solid state has also been determined by an X-ray diffraction study.

Full text of DOI:10.1021/om010005k

2294
Organometallics 2001, 20, 2294-2302
∆2- a n d ∆3-Aza osm etin e Com p lexes a s In ter m ed ia tes in
th e Stoich iom etr ic Im in a tion of P h en yla cetylen e w ith
Oxim es
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 J anuary 2, 2001
Complexes [Os{(E)-CHdCHPh}Cl(dNdCR2)(PiPr3)2][CF3SO3] [CR2
)
CMe2 (1),
C(CH2)4CH2 (2)] react with carbon monoxide to give the ∆2-1,2-azaosmetine derivatives
[OsCl(dCHCH(Ph)NdCR2}(CO)(PiPr3)2][CF3SO3] [CR2 ) CMe2 (3), C(CH2)4CH2 (4)], as a
result of the coordination of carbon monoxide to the osmium atoms of 1 and 2 and the carbon-
nitrogen coupling between the styryl and azavinylidene ligands. The structure of 3 in the
solid state has been determined by an X-ray diffraction study. Complexes 3 and 4 can be
deprotonated with MeLi to give the ∆3-1,2-azaosmetine compounds Os{CHdC(Ph)Nd
CR2}Cl(CO)(PiPr3)2 [CR2 ) CMe2 (5), C(CH2)4CH2 (6)], which react with molecular hydrogen
to afford the 2-aza-1,3-butadienes CH2dC(Ph)NdCR2 [CR2 ) CMe2 (7), C(CH2)4CH2 (8)] and
OsH2(η2-H2)(CO)(PiPr3)2. The carbonylation of the cations of 3 and 4 leads to [Os{(Z)-CHd
C(Ph)NHdCR2}Cl(CO)2(PiPr3)2]+ [CR2 ) CMe2 (9), C(CH2)4CH2 (10)]. The [BF4]- salts of 9
and 10 have been obtained by carbonylation of 5 and 6 and subsequent protonation of the
resulting η1-azabutadiene intermediates Os{(Z)-CHdC(Ph)NdCR2}Cl(CO)2(PiPr3)2 [CR2 )
CMe2 (11), C(CH2)4CH2 (12)]. The structure of the [BF4]- salt of 10 in the solid state has
also been determined by an X-ray diffraction study.
In tr od u ction
dienes play a prominent role, as has been shown by
Barluenga and co-workers.6 This type of heterodienes
are able to react with typical electron-deficient dieno-
philes in Diels-Alder reactions. Their utility in organic
synthesis is indicated not only in cycloaddition reactions
but also in other types of processes such as cyclo-
condensation reactions, halogenations, etc.6b,7 At first
glance, a direct and general synthetic strategy to obtain
2-aza-1,3-dienes should be the addition of N-protio
The hydroamination of alkenes and alkynes in the
presence of transition-metal complexes is an attractive
route to prepare numerous classes of organo-nitrogen
molecules.1 Two basic approaches have been employed.
They involve either alkene/alkyne or amine activation
routes.2 Alkene/alkyne activation is generally accom-
plished with late-transition-metal complexes, which
render coordinated olefins/alkynes more susceptible to
attack by exogeneous amine-nucleophiles.3 The alterna-
tive amine activation route uses N-H oxidative addition
to electron-rich late-transition-metal centers.4 Recently,
it has been shown that alkyne-cycloaddition reactions
on early-transition-metal-nitrogen multiple bonds, to
afford azametallacyclobutenes, are also important mecha-
nistic steps in the amination of alkynes.5
(5) (a) Walsh, P. J .; Hollander, F. J .; Bergman, R. G. J . Am. Chem.
Soc. 1988, 110, 8729. (b) Vaughan, G. A.; Hillhouse, G. L.; Rheingold,
A. L. J . Am. Chem. Soc. 1990, 112, 7994. (c) Walsh, P. J .; Baranger,
A. M.; Bergman, R. G. J . Am. Chem. Soc. 1992, 114, 1708. (d) de With,
J .; Horton, A. D.; Orpen, A. G. Organometallics 1993, 12, 1493. (e)
Baranger, A. M.; Walsh, P. J .; Bergman, R. G. J . Am. Chem. Soc. 1993,
115, 2753. (f) Walsh, P. J .; Hollander, F. J .; Bergman, R. G. Organo-
metallics 1993, 12, 3705. (g) Lee, S. Y.; Bergman, R. G. Tetrahedron
1995, 51, 4255. (h) Meyer, K. E.; Walsh, P. J .; Bergman, R. G. J . Am.
Chem. Soc. 1995, 117, 974. (i) Hanna, T. A.; Baranger, A. M.; Walsh,
P. J .; Bergman, R. G. J . Am. Chem. Soc. 1995, 117, 3292. (j) Hanna,
T. A.; Baranger, A. M.; Bergman, R. G. J . Org. Chem. 1996, 61, 4532.
(k) Li, Y.; Marks, T. J . J . Am. Chem. Soc. 1998, 120, 1757. (l)
Arredondo, V. M.; McDonald, F. E.; Marks, T. J . J . Am. Chem. Soc.
1998, 120, 4871. (m) Polse, J . L.; Andersen, R. A.; Bergman, R. G. J .
Am. Chem. Soc. 1998, 120, 13405. (n) Harlan, C. J .; Tunge, J . A.;
Bridgewater, B. M.; Norton, J . R. Organometallics 2000, 19, 2365. (o)
Zuckerman, R. L.; Krska, S. W.; Bergman, R. G. J . Am. Chem. Soc.
2000, 122, 751.
Among the group of organo-nitrogen molecules widely
used as intermediates in organic synthesis, 2-aza-1,3-
(1) Mu¨ller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675.
(2) (a) Taube, R. In Applied Homogeneous Catalysis with Organo-
metallic Compounds; Cornils, B., Herrman, W. A., Eds.; VCH: Wein-
heim, 1996; Vol. 1, 507. (b) Burling, S.; Field, L. D.; Messerle, B. A.
Organometallics 2000, 19, 87.
(3) See for example: (a) Beller, M.; Eichberger, M.; Trauthwein, H.
Angew. Chem., Int. Ed. Engl. 1997, 36, 2225. (b) Kawatsura, M.;
Hartwig, J . F. J . Am. Chem. Soc. 2000, 122, 9546.
(4) See for example: (a) Casalnuovo, A. L.; Calabrese, J . C.; Milstein,
D. J . Am. Chem. Soc. 1988, 110, 6738. (b) Uchimaru, Y. Chem.
Commun. 1999, 1133.
(6) See for example: (a) Barluenga, J .; J oglar, J .; Gonza´lez, F. J .;
Fustero, S. Synlett 1990, 129. (b) Barluenga, J .; Aznar, F.; Fustero,
S.; Toma´s, M. Pure Appl. Chem. 1990, 62, 1957.
(7) (a) Georg, G. I.; He, P.; Kant, J .; Mudd, J . Tetrahedron Lett. 1990,
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58, 5771.
10.1021/om010005k CCC: $20.00 © 2001 American Chemical Society
Publication on Web 05/04/2001

∆2- and ∆3-Azaosmetine Complexes
Organometallics, Vol. 20, No. 11, 2001 2295
Sch em e 1
imines to nonactivated alkynes, in the presence of a
transition-metal complex. However, although organic
chemists have developed various synthetic aproaches,8
this route has not been investigated.
The use of N-protio imines as amination reagents has
a serious limitation, the known low stability of the
N-protio ketimines.9 With the aim of finding an alterna-
tive, two years ago we initiated a research program
centered in the use of oximes. It was known from work
in our group that the use of transition-metal complexes
with several hydrogen atoms bonded to the metallic
center, first, allows the access of several organic mol-
ecules into the metal; second, this access can be sequen-
tial and selective; and third, a wide range of organo-
metallic functional groups can be obtained. All this
facilitates different types of coupling reactions and the
generation of organic fragments with a rich organic
chemistry, which permits the growth of the ligands.10
These precedents prompted us to study the reac-
tions of the dihydride-dichloro complex OsH2Cl2(PiPr3)2
with acetone oxime, cyclohexanone oxime, and phenyl-
acetylene. In an initial stage, the oximes were intro-
duced into the metallic center11 and the oxygen atom
was eliminated by reaction of the resulting oximate
compounds with HCl12 (Scheme 1). The alkyne was
introduced into the osmium atom by treatment of
Sch em e 2
OsHCl2(dNdCR2)(PiPr3)2 [CR2 ) CMe2, C(CH2)4CH2]
with Ag[CF3SO3] at room temperature and the subse-
quent addition of phenylacetylene at -25 °C. Then, we
attempted the coupling of the alkenyl and azavinylidene
ligands of [Os{(E)-CHdCHPh}Cl(dNdCR2)(PiPr3)2]+ by
means of the additions of NaCl, H2O, and CH3CN.
However, the formation of the imine-vinylidene deriva-
tives OsCl2(dCdCHPh)(NHdCR2)(PiPr3)2 and [OsCl(d
CdCHPh)(NHdCR2)L(PiPr3)2]+ (L ) H2O, CH3CN) was
observed, as a result of the novel hydrogen transfer from
the styryl ligands to the azavinylidene groups.13 We
(8) (a) Barluenga, J .; J oglar, J .; Fustero, S.; Gotor, V.; Kru¨ger, C.;
Roma˜o, M. J . Chem. Ber. 1985, 118, 3652. (b) Chen, S.-F.; Mariano, P.
S. Tetrahedron Lett. 1985, 26, 47. (c) Barluenga, J .; Ferrero, M.;
Palacios, F. Tetrahedron Lett. 1990, 31, 3497. (d) Ghosez, L.; Bayard,
Ph.; Nshimyumukiza, P.; Gouverneur, V.; Sainte, F.; Beaudegnies, R.;
Rivera, M.; Frisque-Hesbain, A.-M.; Wynants, C. Tetrahedron 1995,
51, 11021. (e) Palacios, F.; Alonso, C.; Rubiales, G. J . Org. Chem. 1997,
62, 1146. (f) Palacios, F.; Gil, M. J .; Mart´ınez de Marigorta, E.;
Rodr´ıguez, M. Tetrahedron Lett. 1999, 40, 2411.
(9) (a) March, J . Advanced Organic Chemistry: Reactions, Mecha-
nisms, and Structure; McGraw-Hill Book Co.: New York, 1968;
Chapter 16, p 656. (b) Robertson, G. M. In Comprehensive Organic
Functional Group Transformations; Katritzley, A. R., Meth-Cohn, O.,
Rees, C. W., Eds.; Pergamon: Oxford, England, 1995; Vol. 3, pp 403-
432.
have now observed that, in contrast to NaCl, H2O, and
CH3CN, carbon monoxide promotes the coupling of the
styryl and azavinylidene ligands.
In this paper, we report the remaining steps to obtain
2-aza-1,3-dienes, as well as the characterization of the
organometallic intermediates, including ∆2-1,2- and ∆3-
1,2-azaosmetine derivatives.
Resu lts a n d Discu ssion
(10) See for example: (a) Espuelas, J .; Esteruelas, M. A.; Lahoz, F.
J .; Oro, L. A.; Valero, C. Organometallics 1993, 12, 663. (b) Esteruelas,
M. A.; Lahoz, F. J .; Lo´pez, A. M.; On˜ate, E.; Oro, L. A. Organometallics
1994, 13, 1669. (c) Esteruelas, M. A.; Liu, F.; On˜ate, E.; Sola, E.; Zeier,
B. Organometallics 1997, 16, 2919. (d) Buil, M. L.; Esteruelas, M. A.;
Lo´pez, A. M.; On˜ate, E. Organometallics 1997, 16, 3169. (e) Bohanna,
C.; Callejas, B.; Edwards, A. J .; Esteruelas, M. A.; Lahoz, F. J .; Oro,
L. A.; Ruiz, N.; Valero, C. Organometallics 1998, 17, 373. (f) Bohanna,
C.; Buil, M. L.; Esteruelas, M. A. On˜ate, E.; Valero, C. Organometallics
1999, 18, 5176. (g) Bernad, D. J .; Esteruelas, M. A.; Lo´pez, A. M.;
Oliva´n, M.; On˜ate, E.; Puerta, M. C.; Valerga, P. Organometallics 2000,
19, 4327, and references therein. (h) Esteruelas, M. A.; Garc´ıa-Yebra,
C.; Oliva´n, M.; On˜ate, E.; Tajada, M. A. Organometallics 2000, 19,
5098.
1. Cou p lin g betw een th e Alk en yl a n d Aza vin yl-
id en e Liga n d s of [Os{(E)-CHdCHP h }Cl(dNdCR2)-
(P iP r 3)2][CF 3SO3] [CR2 ) CMe2, C(CH2)4CH2]. Under
atmospheric pressure of carbon monoxide, complexes
[Os{(E)-CHdCHPh}Cl(dNdCR2)(PiPr3)2][CF3SO3] [CR2
) CMe2 (1), C(CH2)4CH2 (2)], in 1:1 mixtures of dichloro-
methane/diethyl ether as solvent, afford after 1 h the
∆2-1,2-azaosmetine derivatives [OsCl{dCHCH(Ph)Nd
(11) 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.
(12) 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.
(13) Castarlenas, R.; Esteruelas, M. A.; On˜ate, E. Organometallics
2000, 19, 5454.
CR2}(CO)(PiPr3)2][CF3SO3] [CR2 ) CMe2 (3), C(CH2)4CH2
(4)], which were isolated as yellow solids in about 80%
yield.
The formation of these compounds can be rationalized
as intramolecular [2+2] cycloaddition reactions between

2296 Organometallics, Vol. 20, No. 11, 2001
Castarlenas et al.
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex
[OsCl{dHCH(P h )NdCMe2}(CO)(P iP r 3)2][CF 3SO3] (3)
Os-Cl
2.500(2)
1.890(10)
1.854(10)
2.260(7)
2.496(2)
Os-P(2)
N-C(1)
2.487(2)
Os-C(4)
Os-C(30)
Os-N
1.301(11)
1.497(10)
1.520(13)
1.542(12)
N-C(5)
C(4)-C(5)
C(5)-C(6)
Os-P(1)
P(1)-Os-P(2)
P(1)-Os-N
167.17(8)
92.9(2)
84.86(17)
88.1(3)
93.84(18)
96.84(18)
160.4(4)
65.6(3)
Cl-Os-C(30)
Cl-Os-C(4)
C(30)-Os-C(4)
Os-N-C(1)
102.7(3)
162.3(3)
94.8(4)
145.4(6)
90.8(5)
97.6(7)
105.7(6)
115.8(8)
P(1)-Os-Cl
P(1)-Os-C(30)
P(1)-Os-C(4)
N-Os-Cl
Os-N-C(5)
N-C(5)-C(4)
Os-C(4)-C(5)
C(2)-C(1)-C(3)
N-Os-C(30)
N-Os-C(4)
The four atoms Os, C(4), C(5), and N forming the
heterometallacycle and the iminic atoms C(1), C(2), and
C(3) are almost planar. The deviations from the plane
are -0.150 Å (Os), 0.03 Å [C(4)], 0.09 Å [C(5)], 0.10 Å
[N], -0.16 Å [C(1)], -0.16 Å [C(2)], and 0.08 Å [C(3)].
In agreement with the distances and angles found in
osmium-carbene compounds,14 the Os-C(4) bond length
and the Os-C(4)-C(5) angle are 1.890(10) Å and
105.7(6)°, respectively. The C(4)-C(5) distance [1.520(13)
Å] agrees well with the average of the C(sp2)-C(sp3)
single bond distances [1.48(3) Å],15 whereas the N-C(5)
bond length [1.497(10) Å] supports the C-N single bond
formulation and is about 0.2 Å longer than the N-C(1)
distance [1.301(11) Å]. The latter is similar to the C-N
double bond distances observed in imine transition
metal complexes,16 azavinylidene compounds,17 organic
azaallenium cations,18 and 2-azaallenyl complexes.19
The Os-N bond length [2.260(7) Å], which is about 0.2
Å longer than those found in the imine complexes
F igu r e 1. Molecular diagram for [OsCl{dCHCH(Ph)Nd
CMe2}(CO)(PiPr3)2]+ (3). Thermal ellipsoids are shown at
50% probability.
the osmium-azavinylidene bonds and the carbon-
carbon double bond of the styryl ligands (Scheme 2). In
agreement with the lability of the agostic interactions
and with the formation of the previously reported
complexes Os{(E)-CHdCHPh}Cl2(dNdCR2)(PiPr3)2 and
[Os{(E)-CHdCHPh}Cl(dNdCR2)L(PiPr3)2][CF3SO3]
(L ) H2O, CH3CN),13 the first step of these transforma-
tions should be the coordination of carbon monoxide
trans to the azavinylidene ligands. Thus, the strong
π-acceptor power of the carbonyl could excite the
π-donor nature of the azavinylidene groups, increasing
the double bond character of the osmium-azavinylidene
bonds and, in this way, activating the intramolecular
cyclization between the Os-N and C-C double bonds.
The very low π-acceptor capacity of the chlorine, water,
and acetonitrile ligands could explain why the above-
mentioned six-coordinate alkenyl-azavinylidene com-
plexes evolve into imine-vinylidene derivatives instead
of ∆2-1,2-azaosmetine compounds. In addition, it should
be noted that the formation of 3 and 4 indicates that
the cycloaddition reactions between metal-nitrogen and
carbon-carbon double bonds can occur not only with
early transition metals but also with late transition
metals, when the latter coordinate π-acidic ligands.
Complexes 3 and 4 were characterized by MS, ele-
(14) (a) Hill, A. F.; Roper, W. R.; Waters, J . M.; Wright, A. H. J .
Am. Chem. Soc. 1983, 105, 5939. (b) Bohle, D. S.; Clark, G. R.; Rickard,
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E.; Oro, L. A.; Valero, C.; Zeier, B. J . Am. Chem. Soc. 1995, 117, 7935.
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E.; Oliva´n, M. Organometallics 2000, 19, 2184.
(15) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
D. G.; Taylor, R. J . Chem. Soc., Dalton Trans. 1989, S1.
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M. J . J . Organomet. Chem. 1991, 420, 237. (b) Knight, D. A.; Dewey,
M. A.; Stark, G. A.; Bennett, B. K.; Arif, A. M.; Gladysz, J . A.
Organometallics 1993, 12, 4523. (c) Yeh, W.-Y.; Ting, C.-S.; Peng, S.-
M.; Lee, G.-H. Organometallics 1995, 14, 1417. (d) Gunnoe, T. B.;
White, P. S.; Templeton, J . L. J . Am. Chem. Soc. 1996, 118, 6916.
(17) See for example: (a) Bochmann, M.; Wilson, L. M.; Hursthouse,
M. B.; Motevalli, M. Organometallics 1988, 7, 1148. (b) Daniel, T.;
Knaup, W.; Dziallas, M.; Werner, H. Chem. Ber. 1993, 126, 1981. (c)
Werner, H.; Daniel, T.; Braun, T.; Nu¨rnberg, O. J . Organomet. Chem.
1994, 480, 145. (d) Powell, K. R.; Pe´rez, P. J .; Luan, L.; Feng, S. G.;
White, P. S.; Brookhart, M.; Templeton, J . L. Organometallics 1994,
13, 1851. (e) Esteruelas, M. A.; Lahoz, F. J .; Oliva´n, M.; On˜ate, E.;
Oro L. A. J . Organometallics 1994, 13, 3315.
(18) (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.
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1
mental analysis, IR, and H, 13C{1H}, and 31P{1H} NMR
spectroscopy. Complex 3 was further characterized by
an X-ray crystallographic study. A view of the molecular
geometry of the cation of the salt is shown in Figure 1.
Selected bond distances and angles are listed in Table
1.
The coordination geometry around the osmium atom
can be rationalized as a distorted octahedron with the
two phosphorus atoms of the phosphine ligands occupy-
ing opposite positions [P(1)-Os-P(2)] ) 167.17(8)°]. The
perpendicular plane is formed by the chlorine and
carbonyl ligands mutually cis disposed [Cl-Os-C(30)
) 102.7(3)°], the heterometallacycle with the nitrogen
atom trans disposed to the carbonyl group [N-Os-C(30)
) 160.4(4)°], and the C(4) atom trans disposed to the
chlorine [Cl-Os-C(4) ) 162.3(3)°].
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∆2- and ∆3-Azaosmetine Complexes
Organometallics, Vol. 20, No. 11, 2001 2297
OsCl2(dCdCHPh)(NHdCMe2)(PiPr3)2 [2.072(7) Å] and
[OsCl(dCdCHPh)(NHdCMe2)(H2O)(PiPr3)2][CF3SO3]
[2.067(5) Å],13 reveals the tension within the four-
membered ring. The angles within the heterometalla-
cycle are between 65.6(3)° [N-Os-C(4)] and 105.7(6)°
[Os-C(4)-C(5)].
constants of about 8 Hz, whereas the dCPh resonances
are observed at about 146 ppm, also as triplets but with
C-P coupling constants of about 3 Hz. The 31P{1H}
NMR spectra contain singlets at about 9 ppm.
The azaosmetine units of 5 and 6 are rings analogous
to the azametallacycle-butenes generated by alkyne-
cycloaddition reactions on early-transition-metal-
nitrogen multiple bonds, and as the latter, they are key
structures during the amination of alkynes. Thus,
complexes 5 and 6 react with molecular hydrogen to give
In agreement with the presence of a carbonyl ligand
in 3 and 4, the IR spectra of these compounds show a
ν(CO) band at 1958 cm-1 in both complexes. In addition,
the spectra contain a ν(CdN) absorption at 1648 (3) and
1625 (4) cm-1, along with the characteristic streching
bands of the free [CF3SO3]- anion20 at about 1264, 1226,
the 2-aza-1,3-butadienes CH2dC(Ph)NdCR2 [CR2
)
CMe2 (7), C(CH2)4CH2 (8)] and the well-known dihy-
dride-dihydrogen complex OsH2(η2-H2)(CO)(PiPr3)2 (eq
2).21
1
1144, and 1036 cm-1. In the H NMR spectra of both
compounds, the most noticeable resonances are two
singlets at 15.84 and 5.49 (3) and 16.57 and 5.77 (4)
ppm, corresponding to the HR and Hâ hydrogen atoms
of the azaosmetine unit. In the 13C{1H} NMR spectra,
the resonances due to the C(sp2) atoms of the hetero-
metallacycle appear at about 273 ppm, as triplets with
C-P coupling constants of about 7 Hz, whereas the
resonances due to C(sp3) atoms of the heterometallacycle
are observed as singlets at about 100 ppm. The 31P{1H}
NMR spectra show AB spin systems at 26.0 and 18.8
(3) and 32.9 and 23.7 (4) ppm, with P-P coupling
constants of about 195 Hz.
2. Relea se of 2-Aza -1,3-bu ta d ien es fr om th e Os-
m iu m Atom . The ∆2-1,2-azaosmetine complexes 3 and
4 can be converted into the ∆3-1,2-azaosmetine deriva-
tives Os{CHdC(Ph)NdCR2}Cl(CO)(PiPr3)2 [CR2 ) CMe2
(5), C(CH2)4CH2 (6)] by deprotonation of the C(sp3)
atoms of the azaosmetine units, with equimolecular
amounts of MeLi in tetrahydrofuran as solvent (eq 1).
The reactions collected in Schemes 1 and 2 and eqs 1
and 2 constitute the pathway for the stoichiometric
amination of phenylacetylene with acetone oxime and
cyclohexanone oxime, in the presence of the dihydride-
dichloro complex OsH2Cl2(PiPr3)2. It should be noted
that the key step of the process is the formation of the
∆2-1,2-azaosmetine intermediates 3 and 4, which ap-
pears to occur by [2+2] cycloadditions similar to those
proposed by the catalytic hydroamination of alkynes
with imido-zirconium complexes.5c,e,g,i Because the
cycloaddition in the stoichiometric process is intra-
molecular instead of intermolecular, as in the catalytic
reaction, the deprotonation of 3 and 4 is necessary to
generate the ∆3-1,2-azaosmetine intermediates 5 and
6, which are analogues to the azametallacycles of
zirconium formed during the catalytic reactions. The
formation of 5 and 6 by deprotonation of 3 and 4,
respectively, is a novel method to form this type of
compounds, which, as well as 3 and 4, were unknown
in the chemistry of late transition metals.
Complexes 5 and 6 were isolated as yellow solids in
about 80% yield. In the IR spectra in KBr of these
compounds, the most noticeable feature is the absence
of any band corresponding to the [CF3SO3]- anion. The
ν(CO) and ν(CdN) absorptions appear at 1887 and 1620
3. ∆2-1,2-Aza osm etin e Ca tion s a s In ter m ed ia tes
in th e F or m a tion of [Os{(Z)-CHdC(P h )NHdCR2}-
Cl(CO)2(P iP r 3)2]+. If the treatment of 1 and 2 with
carbon monoxide is prolonged by more than 1 h, in
addition to 3 and 4, the formation of [Os{(Z)-CHdC(Ph)-
1
(5) and 1889 and 1607 (6) cm-1, respectively. In the H
NMR spectra the resonances due to the Os-CH protons
of the heterometallacycles are observed as singlets at
8.80 (5) and 9.06 (6) ppm. In the 13C{1H} NMR spectra
the resonances due to the Os-C carbon atoms appear
at 149.8 ppm (5 and 6), as triplets with C-P coupling
NHdCR2}Cl(CO)2(PiPr3)2]+ [CR2 ) CMe2 (9), C(CH2)4CH2
(10)] is observed. Complexes 9 and 10 are the result of
(21) (a) Werner, H.; Esteruelas, M. A.; Meyer, U.; Wrackmeyer, B.
Chem. Ber. 1987, 120, 11. (b) Gusev, D. G.; Kuhlman, R. L.; Renkema,
K. B.; Eisenstein, O.; Caulton, K. G. Inorg. Chem. 1996, 35, 663.
(20) Lawrence, G. A. Chem. Rev. 1986, 86, 17.

2298 Organometallics, Vol. 20, No. 11, 2001
Castarlenas et al.
Sch em e 3
Sch em e 4
F igu r e 2. Molecular diagram for [Os{(Z)-CHdC(Ph)NHd
C(CH2)4CH2}Cl(CO)2(PiPr3)2]+ (10). Thermal ellipsoids are
shown at 50% probability.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for th e Com p lex [Os{(Z)-CHdC(P h )NHd
C(CH2)4CH2}Cl(CO)2(P iP r 3)2]BF 4 (10)
Os-C(1)
Os-Cl
Os-C(15)
Os-C(16)
Os-P(1)
Os-P(2)
2.115(9)
2.450(2)
1.938(10)
1.901(11)
2.458(3)
2.445(3)
C(15)-O(1)
C(16)-O(2)
C(1)-C(2)
C(2)-C(9)
C(2)-N
1.152(10)
1.113(10)
1.340(12)
1.494(12)
1.482(11)
1.260(12)
1.525(14)
C(3)-N
C(3)-C(4)
P(1)-Os-P(2)
P(1)-Os-C(1)
P(1)-Os-Cl
172.16(8)
90.8(3)
85.96(10)
89.8(3)
93.3(3)
84.5(3)
C(1)-Os-C(16)
C(15)-Os-C(16)
Os-C(1)-C(2)
C(1)-C(2)-N
C(9)-C(2)-N
C(2)-N-C(3)
N-C(3)-C(4)
93.9(4)
87.4(4)
140.4(7)
114.4(8)
113.0(8)
126.2(10)
117.2(11)
P(1)-Os-C(15)
P(1)-Os-C(16)
C(1)-Os-Cl
C(1)-Os-C(15)
178.5(4)
the carbonylation of 3 and 4 and the 1,2-hydrogen
migration from the CHPh carbon atoms to the nitrogen
atoms (Scheme 3).
The BF4 salts of 9 and 10 can be obtained as pure
microcrystalline solids, starting from 5 and 6, according
to Scheme 4. Under carbon monoxide atmosphere the
heterometallacycles of 5 and 6 are opened, and the
coordination of a carbonyl ligand affords the cis-dicar-
bonyl derivatives Os{(Z)-CHdC(Ph)NdCR2}Cl(CO)2-
sponding to the Os-CH and CPhN carbon atoms are
observed at 139.5 and 150.3 (11) and 140.0 and 149.8
(12) ppm, as triplets with C-P coupling constants of
about 12 (CR) and 4 (Câ) Hz. The 31P{1H} NMR spectra
contain singlets at about 7 ppm.
Complexes 9 and 10 were isolated as white solids in
86% (9) and 83% (10) yield and were characterized by
MS, elemental analysis, IR, and 1H, 13C{1H}, and
31P{1H} NMR spectroscopy. Complex 10 was further
characterized by an X-ray crystallographic study. Figure
2 shows a view of the molecular geometry of this
complex, whereas Table 2 collects selected bond dis-
tances and angles.
The coordination geometry around the osmium atom
can be rationalized as a distorted octahedron with the
two phosphorus atoms of the phosphine ligands occupy-
ing opposite positions [P(1)-Os-P(2) ) 172.16(8)°]. The
perpendicular plane is formed by the carbonyl ligands
mutually cis disposed [C(15)-Os-C(16) ) 87.4(4)°] and
the chlorine and the η1-carbon ligand also cis disposed
[C(1)-Os-Cl ) 84.5(3)°].
The unsaturated η1-carbon ligand shows a Z stereo-
chemistry at the C(1)-C(2) double bond. The Os-C(1)
bond length [2.115(9) Å] compares well with the Os-
C(sp2) single bond distances found in the complexes
(PiPr3)2 [CR2 ) CMe2 (11), C(CH2)4CH2 (12)], which
react with HBF4‚OEt2 to give 9 and 10. The latter are
the result of the protonation of the nitrogen atom of the
unsaturated η1-carbon ligands of 11 and 12.
Complexes 11 and 12 were isolated as yellow solids
in about 80% yield. The IR spectra of these compounds
in KBr show two ν(CO) bands between 2000 and 1920
cm-1. The mutually cis disposition of the carbonyl
ligands is strongly supported by the intensity ratios of
the ν(CO) bands, which suggest angles between the
1
carbonyl ligands of about 90°.22 In the H NMR spectra,
the most noticeable resonance is that due to the Os-
CH proton, which appears at 7.90 ppm as a triplet with
a H-P coupling constant of 2.2 Hz in both compounds.
In the 13C{1H} NMR spectra, the resonances corre-
(22) [I(higher ν)]/[I(lower ν)] ) tan2(θ/2)

∆2- and ∆3-Azaosmetine Complexes
Organometallics, Vol. 20, No. 11, 2001 2299
Sch em e 5
spectra, the Os-CH resonances are observed between
158 and 145 ppm, as triplets with C-P coupling
constants of about 10 Hz, whereas the dCPh resonances
appear between 148 and 139 ppm also as triplets but
with C-P coupling constants of about 4 Hz. The 31P{1H}
NMR spectra show a singlet for each isomer at about
12 (9) and 6 (10) ppm.
Os{(E)-CHdCHPh}Cl(CO)(PiPr3)2 [1.99(1) Å],23 [Os{CHd
C(I)C(O)OCH3}(η6-C6H6)(PiPr3)]+ [2.02(1) Å],24 Os{CHd
CHC(O)OCH3}(C2CO2CH3)(CO)(PiPr3)2 [2.103(4) Å],10a
[Os{C[C(O)OCH3]dCH2}(dCdCdCPh2}(CO)(PiPr3)2]+
[2.146(6) Å],10e and Os{C(CH2Ph)dCHC6H4}(CO)2(PiPr3)2
[2.180(4) Å].10d The C(1)-C(2) distance [1.340(12) Å] is
similar to those found in the above-mentioned com-
pounds and agrees well with the average carbon-
carbon double bond distances [1.32(1) Å].15 The C(2)-N
[1.482(11) Å] and N-C(3) [1.269(12) Å] distances are
statistically identical with the related parameters of 3.
The separations between the osmium atom and the
carbonyl ligands [1.938(10) and 1.901(11) Å], as well as
both C-O distances [1.152(10) and 1.113(10) Å], are also
statistically identical. This suggests that the trans
influence of the chlorine and azoniabutadienyl ligands
is similar.
The IR spectra of 9 and 10 in KBr are consistent with
the structure shown in Figure 2. In agreement with the
presence of a hydrogen atom bonded to the nitrogen
atom of the unsaturated η1-carbon ligands, they show
ν(N-H) bands at about 3310 cm-1. Furthermore, in
accordance with the mutually cis disposition of the
carbonyl ligands, the spectra contain two ν(CO) bands
between 2020 and 1940 cm-1. The salt nature of these
compounds is supported by very strong bands at about
1050 cm-1, corresponding to the [BF4]- anion with Td
symmetry.
Con clu d in g Rem a r k s
We have previously shown that the sequential intro-
duction of oximes, such as acetone oxime and cyclohex-
anone oxime, and phenylacetylene into the osmium
atom of OsH2Cl2(PiPr3)2 affords the azavinylidene-
styryl complexes [Os{(E)-CHdCHPh}Cl(dNdCR2)-
(PiPr3)2]+ [CR2 ) CMe2, C(CH2)4CH2].11-13 This study
reveals that the coordination of carbon monoxide to the
osmium atom of these compounds produces the carbon-
nitrogen coupling between the styryl and azavinylidene
ligands, to give the corresponding ∆2-1,2-azaosmetine
derivatives [OsCl{dCHCH(Ph)NdCR2}(CO)(PiPr3)2]+.
This coupling is the key step to form 2-aza-1,3-buta-
dienes by means of the stoichiometric imination of
phenylacetylene with the above-mentioned oximes, in
the presence of OsH2Cl2(PiPr3)2. Thus we also report
that the deprotonation of the ∆2-1,2-azaosmetine com-
plexes with MeLi affords the ∆3-1,2-azaosmetine com-
pounds Os{CHdC(Ph)NdCR2}Cl(CO)(PiPr3)2, which re-
act with molecular hydrogen to give CH2dC(Ph)NdCR2
In solution, complexes 9 and 10 exist as mixtures of
the isomers a and b shown in Schemes 3 and 4. We
assume that the major isomers are 9a and 10a (66%
and 60%, respectively, in acetone-d6). Isomer 10a is the
one found in the solid state by X-ray diffraction. The
existence of these isomers can be explained by hindered
rotation around the Os-CH axis. Using a molecular
model, it can be easily established that this rotation is
highly impeded by the steric demand of the isopropyl
groups of the phosphine ligands, while the rotation
around the PhC-N axis is free.
[CR2 ) CMe2, C(CH2)4CH2] and OsH2(η2-H2)(CO)-
(PiPr3)2.
The ∆2-1,2-azaosmetine complexes are intermediate
species not only to obtain ∆3-1,2-azaosmetine derivatives
but also to form η1-azoniabutadienyl compounds. Thus,
the carbonylation of [OsCl{dCHCH(Ph)NdCR2}(CO)-
(PiPr3)2]+ produces the ring opening of the ∆2-1,2-
azaosmetine units and the 1,2-hydrogen shift from the
CHPh carbon atom to the nitrogen, to give [Os{(Z)-CHd
C(Ph)NHdCR2}Cl(CO)2(PiPr3)2]+. These compounds are
also obtained starting from the ∆3-1,2-azaosmetine
complexes by initial carbonylation and subsequent
protonation of the resulting η1-azabutadienyl derivatives
Os{(Z)-CHdC(Ph)NdCR2}Cl(CO)2(PiPr3)2.
1
In the H NMR spectra, each isomer gives rise to a
NH resonance between 14 and 11 ppm and an Os-CH
resonance between 9 and 8 ppm. In the 13C{1H} NMR
(23) Werner, H.; Esteruelas, M. A.; Otto, H. Organometallics 1986,
5, 2296.
(24) Werner, H.; Weinand, R.; Otto, H. J . Organomet. Chem. 1986,
307, 49.
In conclusion, 2-aza-1,3-butadienes can be obtained
by stoichiometric imination of phenylacetylene with
oximes in the presence of OsH2Cl2(PiPr3)2 (Scheme 5).

2300 Organometallics, Vol. 20, No. 11, 2001
Castarlenas et al.
The process involves ∆2- and ∆3-1,2-azaosmetine inter-
mediates, two novel types of heterometallacyclobutene
derivatives, which were unknown in the chemistry of
the late transition metals.
was concentrated to dryness, addition of methanol led to the
precipitation of a yellow solid, which was washed with
methanol (2 × 2 mL) and dried in vacuo. Yield: 80 mg (80%).
Anal. Calcd for C30H54NClOOsP2: C, 49.20; H, 7.43; N, 1.91.
Found: C, 48.90; H, 7.47; N, 1.82. IR (KBr, cm-1): ν(CO) 1887
(s); ν(CdN) 1620 (m). 1H NMR (C6D6, 20 °C): δ 8.80 (s, 1H,
Os-CH); 7.11 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 6.95 (t, J H-H ) 6.9,
1H, Hpara-Ph); 6.90 (d, J H-H ) 7.8, 2H, Hortho-Ph); 2.66 (m, 6H,
PCH); 2.42 and 1.30 (both s, 6H, {CH3}2CdN); 1.46 and 1.13
(both dvt, J H-H ) 6.9, N ) 13.5, 36H, PCHCH3). 13C{1H} NMR
plus DEPT (C6D6, 20 °C): δ 187.2 (t, J C-P ) 11.5, CO); 164.3
(s, CdN); 149.8 (t, J C-P ) 8.3, Os-CHdCPhN); 145.7 (d, J C-P
) 2.5, Os-CHdCPhN); 141.9 (s, Cipso-Ph); 128.2, 125.5, and
125.0 (all s, CPh); 29.1 and 27.7 (both s, {CH3}2CdN); 24.3 (vt,
N ) 23.1, PCH); 20.7 and 19.7 (both s, PCHCH3). 31P{1H} NMR
(C6D6, 20 °C): δ 9.3 (s). MS (FAB+): m/z 733 (M+).
Exp er im en ta l Section
All reactions were carried out with rigorous exclusion of air
using Schlenk-tube techniques. Solvents were dried by the
usual procedures and distilled under argon prior to use. The
starting materials [Os{(E)-CHdCHPh}Cl(dNdC(CH3)2)-
(PiPr3)2][CF3SO3] (1) [Os{(E)-CHdCHPh}Cl{dNdC(CH2)4-
CH2}(PiPr3)2][CF3SO3] (2) were prepared by the published
method.13 1H NMR spectra were recorded at 300 MHz, and
chemical shifts are expressed in ppm downfield from Me4Si.
13C{1H} NMR spectra were recorded at 75.4 MHz, and chemi-
cal shifts are expressed in ppm downfield from Me4Si.
31P{1H}NMR spectra were recorded at 121.4 MHz, and chemi-
cal shifts are expressed in ppm downfield from 85% H3PO4.
Coupling constants, J and N, are given in hertz.
P r ep a r a tion of Os{CHdC(P h )NdC(CH2)4CH2}Cl(CO)-
(P iP r 3)2 (6). This complex was prepared as described for 5
starting from 200 mg (0.217 mmol) of 4 and 136 µL of a 1.6 M
solution of methyllithium in diethyl ether (0.217 mmol).
Yield: 130 mg (77%). Anal. Calcd for C33H58NClOOsP2: C,
51.31; H, 7.57; N, 1.81. Found: C, 51.24; H, 7.64; N, 1.72. IR
(KBr, cm-1): ν(CO) 1889 (s); ν(CdN) 1607 (m). 1H NMR (C6D6,
20 °C): δ 9.06 (s, 1H, Os-CH); 7.12 (t, J H-H ) 7.8, 2H,
P r ep a r a tion of [OsCl{dCHCH(P h )NdC(CH3)2}(CO)-
(P iP r 3)2][CF 3SO3] (3). A green solution of 1 (100 mg, 0.117
mmol) in 5 mL of a mixture of dichloromethane and diethyl
ether (1:1) was stirred for 1 h under carbon monoxide
atmosphere. The resulting yellow suspension was washed with
diethyl ether (2 × 2 mL) and dried in vacuo. Yield: 85 mg
(82%). Anal. Calcd for C31H55NSClF3O4OsP2: C, 42.19; H, 6.28;
N, 1.58; S, 3.62. Found: C, 41.96; H, 6.17; N, 1.65; S 3.35. IR
(KBr, cm-1): ν(CO) 1958 (s); ν(CdN) 1648 (m); νa(SO3) 1264
(s); νs(CF3) 1226 (s); νa(CF3) 1144 (s); νs(SO3) 1036 (s); δa(SO3)
637 (s). 1H NMR (CD2Cl2, 20 °C): δ 15.84 (s, 1H, OsdCH);
7.33 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 7.20 (t, J H-H ) 7.5, 1H,
H
meta-Ph); 6.96 (d, J H-H ) 7.2, 2H, Hortho-Ph); 6.71 (t, J H-H )
7.5, 1H, Hpara-Ph); 3.18 (m, 2H, {CH2}CdN); 2.82 (m, 6H, PCH);
1.87 (m, 2H, {CH2}CdN); 1.7-1.4 (m, 6H, Cy); 1.49 and 1.18
(both dvt, J H-H ) 6.9, N ) 13.5, 36H, PCHCH3). 13C{1H} NMR
plus DEPT (C6D6, 20 °C): δ 187.0 (t, J C-P ) 11.0, CO); 170.3
(s, CdN); 149.8 (t, J C-P ) 7.8, Os-CHdCPhN); 145.9 (t, J C-P
) 4.1, Os-CHdCPhN); 142.3 (s, Cipso-Ph); 128.5, 124.9, and
124.7 (all s, CPh); 37.4, 36.6, 27.0, and 25.5 (all s, Cy); 24.9 (vt,
N ) 23.0, PCH); 20.7 and 19.8 (both s, PCHCH3). 31P{1H} NMR
(C6D6, 20 °C): δ 9.1 (s). MS (FAB+): m/z 773 (M+) and 738
(M+ - Cl).
H
para-Ph); 7.09 (d, J H-H ) 7.5, 2H, Hortho-Ph); 5.49 (s, 1H, PhCH-
N); 2.76 and 2.19 (both s, 6H, {CH3}2CdN); 2.62 (m, 6H, PCH);
1.4-1.1 (m, 30H, PCHCH3); 0.8-0.6 (m, 6H, PCHCH3).
13C{1H} NMR plus DEPT (CD2Cl2, 20 °C): δ 271.7 (t, J C-P
)
P r epar ation of H2CdC(P h )NdC(CH3)2 (7). A slow stream
of H2 was bubbled through a yellow solution of 5 (40 mg, 0.054
mmol) in 0.5 mL of benzene-d6 in a NMR tube for 5 min, and
then the NMR tube was sealed under H2 atmosphere. After 5
h the quantitative formation of OsH2(η2-H2)(CO)(PiPr3)2 and
7.2, OsdC); 190.7 (s, CdN); 179.6 (t, J C-P ) 10.4, CO); 131.7
(s, Cipso-Ph); 129.0, 128.2, and 124.8 (all s, CPh); 120.5 (q, J C-F
) 320.0, CF3); 100.7 (s, OsdCH-CHPhN); 27.3 and 25.6 (both
s, {CH3}2CdN); 24.6-23.4 (m, PCH); 19.3-16.9 (all s, PCHCH3).
31P{1H} NMR (CD2Cl2, 20 °C): δ AB spin system (δA ) 26.0,
δB ) 18.8, J P-P ) 194.0). MS (FAB+): m/z 734 (M+).
1
7 was determined by H, 13C{1H}, and 31P{1H} NMR spectros-
copy. The solution was transferred to a Schlenk-tube and was
concentrated to dryness. Compound 7 was extracted with
pentane (2 × 2 mL), and the solvent was removed to afford an
P r ep a r a t ion of [OsCl{dCH CH (P h )NdC(CH 2)4CH 2}-
(CO)(P iP r 3)2][CF 3SO3] (4). This complex was prepared as
described for 3 starting from 100 mg (0.112 mmol) of 2. Yield:
84 mg (81%). Anal. Calcd for C34H59NSClF3O4OsP2: C, 44.27;
H, 6.45; N, 1.52; S, 3.48. Found: C, 44.64; H, 6.64; N, 1.72; S,
3.76. IR (KBr, cm-1): ν(CO) 1958 (s); ν(CdN) 1625 (m); νa(SO3)
1262 (s); νs(CF3) 1223 (s); νa(CF3) 1144 (s); νs(SO3) 1033 (s);
δa(SO3) 637 (s). 1H NMR (CD2Cl2, 20 °C): δ 16.57 (s, 1H,
1
orange oil. H NMR (C6D6, 20 °C): δ 7.61 (d, J H-H ) 7.8, 2H,
H
ortho-Ph); 7.2-7.1 (m, 3H, HPh); 4.99 and 4.33 (both s, 2H,
dCH2); 1.87 and 1.52 (both s, 6H, {CH3}2CdN). 13C{1H} NMR
plus DEPT (C6D6, 20 °C): δ 170.7 (s, CdN); 137.7 (s, Cipso-Ph);
127.7 (s, dCPhN); 130.0, 129.3, and 125.8 (all s, CPh); 94.0 (s,
dCH2); 23.8 and 20.2 (both s, {CH3}2CdN). MS (EI): 159 (M+),
103 (M+ - NdC(CH3)2.
OsdCH); 7.48 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 7.38 (d, J H-H
)
P r ep a r a tion of H2CdCP h NdC(CH2)4CH2 (8). This com-
pound was prepared as described for 7 starting from 6 (40 mg,
0.051 mmol). 1H NMR (C6D6, 20 °C): δ 7.62 (d, J H-H ) 7.8,
2H, Hortho-Ph); 7.2-7.1 (m, 3H, HPh); 4.98 and 4.36 (both s, 2H,
dCH2); 2.5-1.9 (m, 10H, Cy). 13C{1H} NMR plus DEPT (C6D6,
20 °C): δ 172.8 (s, CdN); 138.2 (s, Cipso-Ph); 128.2 (s, dCPhN);
129.4, 128.6, and 125.5 (all s, CPh); 93.7 (s, dCH2); 39.1, 30.6,
7.2, 2H, Hortho-Ph); 7.35 (t, J H-H ) 7.5, 1H, Hpara-Ph); 5.77 (s,
1H, PhCH-N); 3.6-3.5 (m, 4H, {CH2}2CdN); 2.82 (m, 6H,
PCH); 1.8-1.2 (m, 36H, PCHCH3 and Cy); 0.9-0.7 (m, 6H,
PCHCH3). 13C{1H} NMR plus APT (CD2Cl2, 20 °C): δ 275.5
(t, J C-P ) 6.5, OsdC); 194.1 (s, CdN); 179.2 (t, J C-P ) 10.5,
CO); 132.2 (s, Cipso-Ph); 127.3, 126.9, and 124.0 (all s, CPh); 120.5
(q, J C-F ) 320.0, CF3); 99.0 (s, OsdCH-CHPhN); 34.6 and 33.7
(both s, {CH2}2CdN); 25.5, 25.4, and 24.0 (all s, Cy); 26.1-
22.6 (m, PCH); 18.3-16.7 (all s, PCHCH3). 31P{1H} NMR
(CD2Cl2, 20 °C): δ AB spin system (δA ) 32.9, δB ) 23.7, J P-P
) 196.0). MS (FAB+): m/z 774 (M+).
27.8, 27.6, and 25.9 (all s, Cy). MS (EI): 199 (M+), 103 (M+
-
NdC(CH2)4CH2).
P r ep a r a t ion of [Os{(Z)-CH dC(P h )NH dC(CH 3)2}Cl-
(CO)2(P iP r 3)2]BF 4 (9). A pale yellow solution of 11 (125 mg,
0.164 mmol) in diethyl ether was treated with tetrafluoroboric
acid (22 µL, 0.165 mmol, 54% in diethyl ether). After 15 min
a white precipitate was formed, which was washed with diethyl
ether (2 × 3 mL) and dried in vacuo. The resulting white
microcrystalline solid was found to be (NMR techniques) a
mixture of two rotamers (ratio a :b ) 2:1). Yield: 120 mg (86%).
Anal. Calcd for C31H55NBClF4O2OsP2: C, 43.90; H, 6.54; N,
P r epar ation of Os{CHdC(P h )NdC(CH3)2}Cl(CO)(P iP r 3)2
(5). A yellow suspension of 3 (120 mg, 0.136 mmol) in 10 mL
of THF was treated with 85 µL of a solution 1.6 M of
methyllithium in diethyl ether (0.136 mmol). A solution was
obtained immediately, and after 5 min the solvent was
evaporated to dryness. Then 10 mL of toluene was added to
eliminate by filtration the LiCF3SO3 formed. After the solution

∆2- and ∆3-Azaosmetine Complexes
Organometallics, Vol. 20, No. 11, 2001 2301
Ta ble 3. Cr ysta l Da ta a n d Da ta Collection a n d Refin em en t for Com p lexes
[OsCl{dCHCH(P h )NdCMe2}(CO)(P iP r 3)2][CF 3SO3] (3) a n d
[Os{(Z)-CHdC(P h )NHdC(CH2)4CH2}Cl(CO)2(P iP r 3)2]BF 4 (10)
3
10
formula
C
31H55ClF3NO4OsP2S
C34H59BClF4NO2OsP‚
0.9CH2Cl20.4THF 0.25C4H10
729.78
irregular block
monoclinic, P21/n
10.887(3)
31.389(8)
14.117(4)
97.210(7)
4806(2)
O
mol wt
color and habit
space group
a, Å
b, Å
c, Å
882.41
irregular block
monoclinic, P21/c
13.748(2)
16.540(3)
17.438(12)
100.795(6)
3895.1(11)
4
â, deg
V, Å3
Z
D
4
calc, g cm-3
1.505
1.391
Data Collection and Refinement
diffractometer
λ(Mo KR), Å
monochromator
µ, mm-1
Bruker-Siemens P4
Bruker-Siemens CCD
0.71073
graphite oriented
3.525
ω/2θ
5 e 2θ e 50
296.0(2)
2.922
scan type
ω scans at different æ values
5 e 2θ e 55
173.0(2)
2θ range, deg
temp, K
no. of data collect
7644
31 470
(h: -16, 1; k: -19, 1;
(h: -14, 10; k: -40, 40;
l: -20, 20)
l: -11, 18)
no. of unique data
6803 (merging R factor 0.0374)
10 932 (merging R factor 0.1345)
no. of params refined
439
501
a
R1 [F2 > 2σ(F2)]
0.0645
0.1321
1.021
0.0645
0.1562
0.794
b
wR2 [all data]
Sc [all data]
a
b
2
2
R1(F) ) ∑||Fo| - |Fc||/∑|Fo|. wR2(F2) ) {∑[w(Fo - Fc2)2]/∑[w(Fo2)2]}1/2
.
c Goof ) S ) {∑[w(Fo - Fc2)2]/(n - p)}1/2, where n is the
number of reflections, and p is the number of refined parameters.
1.65. Found: C, 44.19; H, 6.77; N, 1.64. IR (KBr, cm-1): ν(N-
H) 3310 (m br); ν(CO) 2018 and 1944 (both s); ν(CdN) 1647
(s); ν(BF4) 1040 (s br). MS (FAB+): m/z 762 (M+). Rotamer a :
1H NMR (acetone-d6, 20 °C): δ 13.76 (br, 1H, N-H); 8.24 (s,
1H, Os-CH); 7.5-7.3 (m, 5H, Ph); 2.90 (m, 6H, PCH); 2.71
and 2.02 (both s, 6H, {CH3}2CdN); 1.49 and 1.43 (both dvt,
J H-H ) 6.9, N ) 13.8, 36H, PCHCH3). 13C{1H} NMR plus APT
(acetone-d6, 20 °C): δ 184.4 (s, CdN); 182.5 and 177.5 (both t,
J C-P ) 7.8, CO); 147.5 (t, J C-P ) 4.2, Os-CHdCPhN); 145.6
(t, J C-P ) 11.0, Os-CHdCPhN); 140.1 (s, Cipso-Ph); 129.7, 128.4,
and 126.0 (all s, CPh); 27.6 and 24.2 (both s, {CH3}2CdN); 25.7
(vt, N ) 25.6, PCH); 19.5 and 19.3 (both s, PCHCH3). 31P{1H}
NMR (acetone-d6, 20 °C): δ 12.5 (s). Rotamer b: 1H NMR
(acetone-d6, 20 °C): δ 11.78 (br, 1H, N-H); 8.93 (s, 1H, Os-
CH); 7.5-7.3 (m, 5H, Ph); 2.90 (m, 6H, PCH); 2.84 and 2.41
(both s, 6H, {CH3}2CdN); 1.51 and 1.33 (both dvt, J H-H ) 7.2,
N ) 13.8, 36H, PCHCH3). 13C{1H} NMR plus APT (acetone-
PCHCH3). 13C{1H} NMR (acetone-d6, 20 °C): δ 189.0 (s, CdN);
182.3 and 177.2 (both t, J C-P ) 7.3, CO); 146.7 (t, J C-P ) 4.1,
Os-CHdCPhN); 145.5 (t, J C-P ) 10.9, Os-CHdCPhN); 140.5
(s, Cipso-Ph); 129.5, 128.0, and 125.2 (all s, CPh); 36.2, 32.9, 26.8,
26.0, and 22.9 (all s, Cy); 25.4 (vt, N ) 25.6, PCH); 19.3 and
19.1 (both s, PCHCH3). 31P{1H} NMR (acetone-d6, 20 °C): δ
1
6.8 (s). Rotamer b: H NMR (acetone-d6, 20 °C): δ 11.15 (br,
1H, N-H); 8.61 (s, 1H, Os-CH); 7.5-7-3 (m, 5H, Ph); 2.63
(m, 6H, PCH); 2.2-1.4 (m, 10H, Cy); 1.25 (m, 36H, PCHCH3).
13C{1H} NMR (acetone-d6, 20 °C): δ 197.0 (s, CdN); 182.8 and
179.3 (both t, J C-P ) 7.3, CO); 157.6 (t, J C-P ) 11.0, Os-CHd
CPhN); 140.0 (s, Cipso-Ph); 139.8 (t, J C-P ) 3.8, Os-CHdCPhN);
129.2, 127.2, and 124.5 (all s, CPh); 36.6, 33.2, 26.7, 26.0, and
23.5 (all s, Cy); 24.6 (vt, N ) 26.1, PCH); 20.1 and 19.2 (both
s, PCHCH3). 31P{1H} NMR (acetone-d6, 20 °C): δ 6.4 (s).
P r ep a r a tion of OsCl{(Z)-CHdC(P h )NdC(CH3)2}(CO)2-
(P iP r 3)2 (11). Carbon monoxide was bubbled through a yellow
solution of 5 (125 mg, 0.171 mmol) in toluene for 15 min. The
solvent was concentrated to dryness, and addition of methanol
led to the precipitation of a pale yellow solid. The solvent was
decanted, and the solid was washed twice with methanol and
then dried in vacuo. Yield: 105 mg (81%). Anal. Calcd for
d6, 20 °C): δ 192.5 (s, CdN); 183.1 and 179.5 (both t, J C-P
)
7.8, CO); 157.6 (t, J C-P ) 10.2, Os-CHdCPhN); 140.8 (t, J C-P
) 4.5, Os-CHdCPhN); 139.2 (s, Cipso-Ph); 129.6, 127.5, and
124.6 (all s, CPh); 26.7 and 24.0 (both s, {CH3}2CdN); 24.9 (vt,
N ) 25.6, PCH); 20.4 and 19.2 (both s, PCHCH3). 31P{1H} NMR
(acetone-d6, 20 °C): δ 11.8 (s).
C
31H54NClO2OsP2: C, 48.97; H, 7.16; N, 1.89. Found: C, 48.75;
H, 7.13; N, 1.82. IR (KBr, cm-1): ν(CO) 1995 and 1926 (both
P r epar ation of [OsCl{(Z)-CHdC(P h )-NHdC(CH2)4CH2}-
(CO)2(P iP r 3)2]BF 4 (10). This complex was prepared as de-
scribed for 9 starting from 125 mg (0.155 mmol) of 12 and
tetrafluoroboric acid (21 µL, 0.157 mmol, 54% in diethyl ether).
The resulting white microcrystalline solid was found to be
(NMR techniques) a mixture of two rotamers (ratio a :b ) 3:2).
Yield: 115 mg (83%). Anal. Calcd for C34H59NBClF4O2OsP2:
C, 45.98; H, 6.70; N, 1.58. Found: C, 45.81; H, 6.62; N, 1.55.
IR (KBr, cm-1): ν(N-H) 3313 (m br); ν(CO) 2009 and 1928
(both s); ν(CdN) 1639 (s); ν(BF4) 1057 (s br). MS (FAB+): m/z
802 (M+). Rotamer a : 1H NMR (acetone-d6, 20 °C): δ 13.31
(br, 1H, N-H); 7.86 (s, 1H, Os-CH); 7.5-7-3 (m, 5H, Ph);
2.63 (m, 6H, PCH); 2.2-1.4 (m, 10H, Cy); 1.25 (m, 36H,
1
s); ν(CdN) 1648 (s). H NMR (C6D6, 20 °C): δ 7.90 (t, J H-P
)
2.2, 1H, Os-CH); 7.51 (d, J H-H ) 8.1, 2H, Hortho-Ph); 7.24 (t,
J H-H ) 7.5, 2H, Hmeta-Ph); 7.02 (t, J H-H ) 7.5, 1H, Hpara-Ph);
2.75 (m, 6H, PCH); 2.01 and 1.45 (both s, 6H, {CH3}2CdN);
1.40 and 1.06 (both dvt, J H-H ) 7.8, N ) 14.7, 36H, PCHCH3).
13C{1H} NMR (C6D6, 20 °C): δ 185.2 and 179.6 (both t, J C-P
)
7.5, CO); 166.1 (s, CdN); 150.3 (t, J C-P ) 4.2, Os-CHdCPhN);
144.4 (t, J C-P ) 1.5, Cipso-Ph); 139.5 (t, J C-P ) 12.0, Os-CHd
CPhN); 128.2, 124.9, and 124.7 (all s, CPh); 27.0 and 23.1 (both
s, {CH3}2CdN); 23.8 (vt, N ) 25.6, PCH); 20.7 and 19.0 (both
s, PCHCH3). 31P{1H} NMR (C6D6, 20 °C): δ 7.2 (s). MS
(FAB+): m/z 761 (M+).

2302 Organometallics, Vol. 20, No. 11, 2001
Castarlenas et al.
frames were collected at the end of the data collection to
monitor crystal decay for 10. The absorption correction was
made using XEMP (3) or SADABS (10).25 The structure was
solved by Multan and Fourier methods using SHELXS.26 Full
matrix least-squares refinement was carried out using
P r ep a r a tion of Os{(Z)-CHdC(P h )NdC(CH2)4CH2}Cl-
(CO)2(P iP r 3)2 (12). This complex was prepared as described
for 11 starting from 125 mg (0.162 mmol) of 6. Yield: 108 mg
(83%). Anal. Calcd for C34H58NClO2OsP2: C, 51.02; H, 7.30;
N, 1.75. Found: C, 50.78; H, 7.55; N, 1.82. IR (KBr, cm-1):
ν(CO) 1996 and 1925 (both s); ν(CdN) 1650 (s). 1H NMR (C6D6,
SHELXL9726 minimizing w(Fo2 - Fc )2. Weighted R factors (Rw)
2
and goodness of fit S are based on F2; conventional R factors
are based on F.
20 °C): δ 7.90 (t, J H-H ) 2.2, 1H, Os-CH); 7.57 (d, J H-H
)
8.1, 2H, Hortho-Ph); 7.25 (t, J H-H ) 7.5, 2H, Hmeta-Ph); 7.03 (t,
J H-H ) 7.2, 1H, Hpara-Ph); 2.78 (m, 6H, PCH); 2.51 (m, 2H,
{CH2}CdN); 2.02 (m, 2H, {CH2}CdN); 1.66 (m, 2H, Cy); 1.42
and 1.10 (both dvt, J H-H ) 6.9, N ) 14.4, 36H, PCHCH3); 1.20
(m, 4H, Cy). 13C{1H} NMR plus DEPT (C6D6, 20 °C): δ 185.3
and 179.7 (both t, J C-P ) 7.5, CO); 171.3 (s, CdN); 149.8 (t,
J C-P ) 3.8, Os-CHdCPhN); 145.5 (s, Cipso-Ph); 140.0 (t, J C-P
) 12.1, Os-CHdCPhN); 128.4 and 124.8 (both s, CPh); 38.7,
34.5, 27.5, 26.2, and 26.0 (all s, Cy); 24.0 (vt, N ) 25.3, PCH);
20.9 and 19.4 (both s, PCHCH3). 31P{1H} NMR (C6D6, 20 °C):
δ 7.6 (s). MS (FAB+): m/z 801 (M+).
The triflate anion of 3 was observed severely disordered and
was refined with three sites for O and F atoms, two sites for
C, and one S atom; restrained geometry and complementary
occupancy factors were also used. 10 crystallizes with mol-
ecules of disordered solvent, modeled as 0.9 molecule of
disordered dichloromethane, 0.4 molecule of THF, and 0.25
molecule of diethyl ether. These molecules were refined with
complementary occupancy factors estimated on thermal pa-
rameters and restrained geometry.
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.
Cr ysta l Da ta for [OsCl{dCHCH(P h )NdC(CH3)2}(CO)-
(P iP r 3)2][CF 3SO3] (3) a n d [OsCl{(Z)-CHdC(P h )-NHd
C(CH2)4CH2}(CO)2(P iP r 3)2]BF 4 (10). A summary of the
fundamental crystal and refinement data of the compounds 3
and 10 is given in Table 3. Crystals of 3 and 10 were mounted
on Bruker P4 (3) and Bruker Smart APEX CCD (10) diffrac-
tometers equipped with a normal focus, 2.4 kW sealed tube
X-ray source (molybdenum radiation, λ ) 0.71073 Å) operating
at 50 kV and 30 mA. Data were collected over a quadrant (3)
or hemisphere (10) by a combination of three sets. The cell
parameters were determined and refined by least-squares fit
of 59 carefully centered high-angle reflections (3) or all
collected reflections (10). Each frame exposure time was 10 s
(10) covering 0.3° in ω (coverage of the unique sets was over
100% complete to at least 25° in θ). Three standard reflections
were monitored through data collection for 3, or the first 100
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates and equivalent isotropic displacement coefficients,
anisotropic thermal parameters, experimental details of the
X-ray studies, and bond distances and angles for 3 and 10.
This material is available free of charge via the Internet at
http://pubs.acs.org.
OM010005K
(25) SHELXTL 6.1 and Smart Apex v. 5; Bruker Analytical X-ray
Systems: Madison, WI, 1997.
(26) Sheldrick, G. M. SHELXS and SHELXL97; University of
Go¨ttingen: Go¨ttingen, Germany, 1997.