Reactions of hydridovanadium complexes: The formation of seven-coordinated σ-alkylvanadium(I) complexes by hydrovanadation of alkenes, and the molecular structure of trans-V(CO)2 (dppe)2] · 3C6D6

Süssmilch, Frank; Olbrich, Falk; Rehder, Dieter

doi:10.1016/0022-328x(94)85015-1

Cited by 10 publications

(3 citation statements)

References 28 publications

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“…4 Nevertheless, medium-valent vanadium hydrides remain rare, 5 despite the promising behavior displayed by some of the few existing examples. 5,6 There is another point of interest that makes the availability of di-and trivalent vanadium hydrides particularly desirable. Trivalent vanadium complexes are used as catalysts for the commercial production of elastomers.…”

Section: Introductionmentioning

confidence: 99%

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Stability of Trivalent Vanadium Alkyl and Hydride Supported by a Chelating Phosphinimido Ligand

et al. 2001

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Reaction of [(Me 3 Si)NdP(Ph) 2 C(H)P(Ph) 2 dN(SiMe 3 )]VCl 2 (1) with 2 equiv of MeLi yielded the corresponding trivalent vanadium derivative [(Me 3 Si)NdP(Ph) 2 C(H)P(Ph) 2 dN(SiMe 3 )]-VMe 2 (3). Subsequent hydrogenolysis afforded the dinuclear hydride complex {[(Me 3 Si)Nd P(Ph) 2 C(H)P(Ph) 2 dN(SiMe 3 )]V} 2 (µ-H) 2 ( 4), where reduction of the metal center to the divalent state had occurred. Hydrogenolysis of solutions of 1 previously treated with lower than stoichiometric amounts of MeLi afforded the two mixed-valent V(II)/V(III) hydrides 7). Hydrolysis of the divalent 4 afforded the trivalent and dinuclear {[(Me 3 Si)NdP(Ph) 2 C(H)P(Ph) 2 d(µ-N)]V(OSiMe 3 )} 2 (5), featuring migration of the Me 3 Si group from the N to the O atom of one incoming molecule of water.

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Section: Introductionmentioning

confidence: 99%

“…Thus, a wealth of reactivity can reasonably be expected for molecular vanadium hydrides also in view of the remarkable behavior displayed by the heavier Nb and Ta congeners . Nevertheless, medium-valent vanadium hydrides remain rare, despite the promising behavior displayed by some of the few existing examples. , …”

Section: Introductionmentioning

confidence: 99%

Stability of Trivalent Vanadium Alkyl and Hydride Supported by a Chelating Phosphinimido Ligand

et al. 2001

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“…Molecular vanadium hydrides are rare species and are exclusively limited to derivatives containing the metal in either medium or low oxidation states. , The insertion of ethylene into the V−H bond, which may in principle lead to polymerization, has so far only been achieved upon photolysis of VH(CO) 5 . Even the simple coordination of an olefin to vanadium is not a straightforward process. , Evidence for labile ethylene coordination was obtained in the case of a cationic pentavalent complex …”

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Oxidative Addition of a Dinuclear and Divalent Vanadium Hydride to an Olefin C−H Bond, Leading to Catalytic Hydrogenation

2001

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The dinuclear and divalent hydride complex {[(Me3Si)NP(Ph)2C(H)P(Ph)2N(SiMe3)]V}2(μ-H)2 (1) performs oxidative addition to the styrene β-C−H bond, affording the novel dinuclear trivalent vanadium complex {[(Me3Si)NP(Ph)2C(H)P(Ph)2N(SiMe3)]V}2(H)(μ-H)2(μ,η1:η2-CHCHPh) (2). Room-temperature hydrogenolysis re-formed 1 and ethylbenzene in catalytic fashion. Reaction of 1 with ethylene afforded instead the mixed-valence {[(Me3Si)NP(Ph)2C(H)P(Ph)2 N(SiMe3)]V}2(μ-H)3 (3) and a mixture of 2-butene and 3-methyl-1,4-pentadiene.

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Vanadium: Organometallic ChemistryBased in part on the article Vanadium: Organometallic Chemistry by Dieter Rehder which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Hirao

2005

Encyclopedia of Inorganic Chemistry

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Reactions of hydridovanadium complexes: The formation of seven-coordinated σ-alkylvanadium(I) complexes by hydrovanadation of alkenes, and the molecular structure of trans-V(CO)2 (dppe)2] · 3C6D6

Cited by 10 publications

References 28 publications

Stability of Trivalent Vanadium Alkyl and Hydride Supported by a Chelating Phosphinimido Ligand

Stability of Trivalent Vanadium Alkyl and Hydride Supported by a Chelating Phosphinimido Ligand

Oxidative Addition of a Dinuclear and Divalent Vanadium Hydride to an Olefin C−H Bond, Leading to Catalytic Hydrogenation

Vanadium: Organometallic ChemistryBased in part on the article Vanadium: Organometallic Chemistry by Dieter Rehder which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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