(η2-vinyl)- and (η3-allyl)tungsten(II) complexes containing a hydridotris(3,5-dimethylpyrazolyl)borate ligand

S. G. Feng, J. L. Templeton

Research output: Research - peer-reviewArticle

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Abstract

Cationic alkyne complexes react with anionic nucleophiles to generate the η2-vinyl complexes Tp′-(CO)2W(η2-RC=CRR′). Reaction of [Tp′(CO)2W(PhC≡CH)][BF4] with P(OMe)3 produces a P(O)(OMe)2-substituted η2-vinyl complex, Tp′(CO)2W[η2-CPh=CHP(O)(OMe)2], which can be protonated at the oxygen to generate a cationic P(OH)(OMe)2-substituted η2-vinyl complex, {Tp′(CO)2W[η2-CPh= CHP(OH)(OMe)2]}[BF4]. Reaction of [Tp′(CO)2W(RC≡CMe)] [BF4] (R = Me, Ph) with LiBEt3H generates η3-allyl complexes via an η2-vinyl intermediate. Reaction of [Tp′(CO)2W(PhC≡CMe)][BF4] with LiCu(Bun)2 yields an η1-acyl complex, Tp′(CO)W(PhC≡CMe)[η1-C(O)Bun], in which the alkyne ligand acts as a four-electron donor.

LanguageEnglish (US)
Pages2168-2175
Number of pages8
JournalOrganometallics
Volume11
Issue number6
StatePublished - 1992

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borates
tungsten
ligands
Borates
Tungsten
Carbon Monoxide
Ligands
alkynes
nucleophiles
methylidyne
oxygen
electrons
Alkynes
Nucleophiles
Oxygen
Electrons

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

(η2-vinyl)- and (η3-allyl)tungsten(II) complexes containing a hydridotris(3,5-dimethylpyrazolyl)borate ligand. / Feng, S. G.; Templeton, J. L.

In: Organometallics, Vol. 11, No. 6, 1992, p. 2168-2175.

Research output: Research - peer-reviewArticle

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abstract = "Cationic alkyne complexes react with anionic nucleophiles to generate the η2-vinyl complexes Tp′-(CO)2W(η2-RC=CRR′). Reaction of [Tp′(CO)2W(PhC≡CH)][BF4] with P(OMe)3 produces a P(O)(OMe)2-substituted η2-vinyl complex, Tp′(CO)2W[η2-CPh=CHP(O)(OMe)2], which can be protonated at the oxygen to generate a cationic P(OH)(OMe)2-substituted η2-vinyl complex, {Tp′(CO)2W[η2-CPh= CHP(OH)(OMe)2]}[BF4]. Reaction of [Tp′(CO)2W(RC≡CMe)] [BF4] (R = Me, Ph) with LiBEt3H generates η3-allyl complexes via an η2-vinyl intermediate. Reaction of [Tp′(CO)2W(PhC≡CMe)][BF4] with LiCu(Bun)2 yields an η1-acyl complex, Tp′(CO)W(PhC≡CMe)[η1-C(O)Bun], in which the alkyne ligand acts as a four-electron donor.",
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N2 - Cationic alkyne complexes react with anionic nucleophiles to generate the η2-vinyl complexes Tp′-(CO)2W(η2-RC=CRR′). Reaction of [Tp′(CO)2W(PhC≡CH)][BF4] with P(OMe)3 produces a P(O)(OMe)2-substituted η2-vinyl complex, Tp′(CO)2W[η2-CPh=CHP(O)(OMe)2], which can be protonated at the oxygen to generate a cationic P(OH)(OMe)2-substituted η2-vinyl complex, {Tp′(CO)2W[η2-CPh= CHP(OH)(OMe)2]}[BF4]. Reaction of [Tp′(CO)2W(RC≡CMe)] [BF4] (R = Me, Ph) with LiBEt3H generates η3-allyl complexes via an η2-vinyl intermediate. Reaction of [Tp′(CO)2W(PhC≡CMe)][BF4] with LiCu(Bun)2 yields an η1-acyl complex, Tp′(CO)W(PhC≡CMe)[η1-C(O)Bun], in which the alkyne ligand acts as a four-electron donor.

AB - Cationic alkyne complexes react with anionic nucleophiles to generate the η2-vinyl complexes Tp′-(CO)2W(η2-RC=CRR′). Reaction of [Tp′(CO)2W(PhC≡CH)][BF4] with P(OMe)3 produces a P(O)(OMe)2-substituted η2-vinyl complex, Tp′(CO)2W[η2-CPh=CHP(O)(OMe)2], which can be protonated at the oxygen to generate a cationic P(OH)(OMe)2-substituted η2-vinyl complex, {Tp′(CO)2W[η2-CPh= CHP(OH)(OMe)2]}[BF4]. Reaction of [Tp′(CO)2W(RC≡CMe)] [BF4] (R = Me, Ph) with LiBEt3H generates η3-allyl complexes via an η2-vinyl intermediate. Reaction of [Tp′(CO)2W(PhC≡CMe)][BF4] with LiCu(Bun)2 yields an η1-acyl complex, Tp′(CO)W(PhC≡CMe)[η1-C(O)Bun], in which the alkyne ligand acts as a four-electron donor.

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