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 W.; Poole, Andrew D.; Siemeling, Ulrich

doi:10.1039/A705197B

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

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Chan, M. C. W., Cole, J. M., Gibson, V. C., Howard, J. A. K., Lehmann, C. W., Poole, A. D., et al. (1998). Half-sandwich imido complexes of niobium bearing alkyne, benzyne and benzylidene ligands: relatives of the zirconocene family. Journal of the Chemical Society, Dalton Transactions, (1), 103-112. doi:10.1039/A705197B.

Cite as: http://hdl.handle.net/11858/00-001M-0000-0024-6FE3-2

Abstract

Reactions of [Nb(C₅H₅)(NC₆H₃Pri₂-2,6)Cl₂] 1a and [Nb(C₅Me₅)(NCH₃Prⁱ₂-2,6)Cl₂] 1b with 1 and 2 equivalents of benzylpotassium respectively gave the niobium benzyl derivatives [Nb(C₅H₅)(NC₆H₃Prⁱ₂-2,6)Cl(CH₂Ph)] 2 and [Nb(C₅Me₅)(NC₆H₃Prⁱ₂-2,6)(CH₂Ph)₂] 3. Treatment of 3 with trimethylphosphine afforded the benzylidene complex [Nb(C₅Me₅)(NC₆H₃Prⁱ₂-2,6)(PMe₃)(=CHPh)] 4. Complex 1a reacted with phenylmagnesium chloride in the presence of PMe₃ to give [Nb(C₅H₅)(NC₆H₃Prⁱ₂-2,6)Ph₂(PMe₃)] 5 which upon heating at 70 °C in heptane, converts to the η²-benzyne complex [Nb(C₅H₅)(NC₆H₃Prⁱ₂-2,6)(η²-C₆H₄)(PMe₃)] 6. The niobium(III) complexes [Nb(CH₅)(NCH₄Bu^t-2)(PMe₃)₂] 8a and [Nb(C₅Me₅)(NCHPrⁱ₂-2,6)(PMe₃)] 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)(PMe₃) (R1 = R2 = Ph 9a; R1 = Ph, R2 = H 9b) and [Nb(C₅Me₅)(NC₆H₃Prⁱ₂-2,6)-(η²-PhC≡CPh)(PMe₃)] 9c upon treatment with the appropriate alkyne. The molecular structures of the 2-tertbutylimido complexes [Nb(C₅H₅)(NCHBu^t-2)Cl₂] 7 and 9a have been determined.