Symmetrically bridged dimeric vanadium nitrido compounds. Synthesis and characterization of [(.eta.-C5Me5)V(N)Cl]2

Haddad, Timothy S.; Aistars, Arnis; Ziller, Joseph W.; Doherty, Nancy M.

doi:10.1021/om00031a008

Cited by 47 publications

(25 citation statements)

References 2 publications

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“…Of the few example, some were derived from N 2 activation 5. 10, 14 The geometrical parameters within the {Nb 2 N 2 } unit of 3 are similar to those found in the known diniobium nitrides 5a. 10…”

Section: Methodssupporting

confidence: 71%

Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species

2007

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Section: Methodssupporting

confidence: 71%

Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species

2007

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“…Of the few example, some were derived from N 2 activation. [5,10,14] The geometrical parameters within the {Nb 2 N 2 } unit of 3 are similar to those found in the known diniobium nitrides. [5a, 10] The nitride complex 3 occurs as an ion pair.…”

Section: Methodssupporting

confidence: 65%

Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species

2007

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“…[10][11][12][13][14] In those reactions, aggregates with diverse nuclearity of titanium, [10][11][12] zirconium, [13] and tantalum [14] containing bulky ancillary ligands (e.g., cyclopentadienyl, alkoxido) at the metal centers have been isolated. In particular, the ability of cyclopentadienyl groups to support metallonitrido oligomers has been proved in vanadium [15] and tantalum [16] compounds …”

Section: Introductionmentioning

confidence: 99%

Molecular Nitrides with Titanium and Group 13–15 Elements

García-Castro¹,

Martı́n²,

Mena³

et al. 2009

Chemistry A European J

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Several heterometallic nitrido complexes were prepared by reaction of the imido-nitrido titanium complex [{Ti(eta(5)-C(5)Me(5))(mu-NH)}(3)(mu(3)-N)] (1) with amido derivatives of Group 13-15 elements. Treatment of 1 with bis(trimethylsilyl)amido [M{N(SiMe(3))(2)}(3)] derivatives of aluminum, gallium, or indium in toluene at 150-190 degrees C affords the single-cube amidoaluminum complex [{(Me(3)Si)(2)N}Al{(mu(3)-N)(2)(mu(3)-NH)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] (2) or the corner-shared double-cube compounds [M(mu(3)-N)(3)(mu(3)-NH)(3){Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] [M = Ga (3), In (4)]. Complexes 3 and 4 were also obtained by treatment of 1 with the trialkyl derivatives [M(CH(2)SiMe(3))(3)] (M = Ga, In) at high temperatures. The analogous reaction of 1 with [{Ga(NMe(2))(3)}(2)] at 110 degrees C leads to [{Ga(mu(3)-N)(2)(mu(3)-NH)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] (5), in which two [GaTi(3)N(4)] cube-type moieties are linked through a gallium-gallium bond. Complex 1 reacts with one equivalent of germanium, tin, or lead bis(trimethylsilyl)amido derivatives [M{N(SiMe(3))(2)}(2)] in toluene at room temperature to give cube-type complexes [M{(mu(3)-N)(2)(mu(3)-NH)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] [M = Ge (6), Sn (7), Pb (8)]. Monitoring the reaction of 1 with [Sn{N(SiMe(3))(2)}(2)] and [Sn(C(5)H(5))(2)] by NMR spectroscopy allows the identification of intermediates [RSn{(mu(3)-N)(mu(3)-NH)(2)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] [R = N(SiMe(3))(2) (9), C(5)H(5) (10)] in the formation of 7. Addition of one equivalent of the metalloligand 1 to a solution of lead derivative 8 or the treatment of 1 with a half equivalent of [Pb{N(SiMe(3))(2)}(2)] afford the corner-shared double-cube compound [Pb(mu(3)-N)(2)(mu(3)-NH)(4){Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] (11). Analogous antimony and bismuth derivatives [M(mu(3)-N)(3)(mu(3)-NH)(3){Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] [M = Sb (12), Bi (13)] were obtained through the reaction of 1 with the tris(dimethylamido) reagents [M(NMe(2))(3)]. Treatment of 1 with [AlCl(2){N(SiMe(3))(2)}(OEt(2))] affords the precipitation of the singular aluminum-titanium square-pyramidal aggregate [{{(Me(3)Si)(2)N}Cl(3)Al(2)}(mu(3)-N)(mu(3)-NH)(2){Ti(3)(eta(5)-C(5)Me(5))(3)(mu-Cl)(mu(3)-N)}] (14). The X-ray crystal structures of 5, 11, 13, 14, and [AlCl{N(SiMe(3))(2)}(2)] were determined.

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Symmetrically bridged dimeric vanadium nitrido compounds. Synthesis and characterization of [(.eta.-C5Me5)V(N)Cl]2

Cited by 47 publications

References 2 publications

Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species

Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species

Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species

Molecular Nitrides with Titanium and Group 13–15 Elements

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