Half-sandwich imido complexes of niobium bearing alkyne, benzyne and benzylidene ligands : Relatives of the zirconocene family

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Jacqueline M. Cole
  • Vernon C. Gibson
  • Judith A. K. Howard
  • Christian Lehmann
  • Andrew D. Poole
  • Ulrich Siemeling

Detail(s)

Original languageEnglish
Pages (from-to)103-111
Journal / PublicationJournal of the Chemical Society - Dalton Transactions
Issue number1
Publication statusPublished - 7 Jan 1998
Externally publishedYes

Abstract

Reactions of [Nb(C5H5)(NC6H3Pri 2-2,6)Cl2] 1a and [Nb(C5Me5)(NC6H3Pri 2-2,6)Cl2] 1b with 1 and 2 equivalents of benzylpotassium respectively gave the niobium benzyl derivatives [Nb(C5H5)(NC6H3Pri 2-2,6)Cl(CH2Ph)] 2 and [Nb(C5Me5)(NC6H3Pri 2-2,6)(CH2Ph)2] 3. Treatment of 3 with trimethylphosphine afforded the benzylidene complex [Nb(C5Me5)(NC6H3Pri 2-2,6)(PMe3)(=CHPh)] 4. Complex 1a reacted with phenylmagnesium chloride in the presence of PMe3 to give [Nb(C5H5)(NC6H3Pri 2-2,6)Ph2(PMe3)] 5 which upon heating at 70°C in heptane, converts to the η2-benzyne complex [Nb(C5H5)(NC6H3Pri 2-2,6)(η2-C6H4)(PMe 3)] 6. The niobium(III) complexes [Nb(C5H5)(NC6H4Bu t-2)(PMe3)2] 8a and [Nb(C5Me5)(NC6H3Pri 2-2,6)(PMe3)2] 8b were obtained upon magnesium reduction of 1a and 1b respectively in the presence of an excess of PMe3. They were converted into [Nb(C5H5)-(NC6H4Bu t-2)(η2-R1C≡CR2)(PMe 3) (R1 = R2 = Ph 9a; R1 = Ph, R2 = H 9b) and [Nb(C5Me5)(NC6H3Pri 2-2,6)-(η2-PhC≡CPh)(PMe3)] 9c upon treatment with the appropriate alkyne. The molecular structures of the 2-tert-butylimido complexes [Nb(C5H5)(NC6H4Bu t-2)Cl2] 7 and 9a have been determined.

Citation Format(s)

Half-sandwich imido complexes of niobium bearing alkyne, benzyne and benzylidene ligands : Relatives of the zirconocene family. / Chan, Michael C. W.; Cole, Jacqueline M.; Gibson, Vernon C.; Howard, Judith A. K.; Lehmann, Christian; Poole, Andrew D.; Siemeling, Ulrich.

In: Journal of the Chemical Society - Dalton Transactions, No. 1, 07.01.1998, p. 103-111.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review