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DOI: 10.1039/A608008A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1719-1726

Hydrazido(2-) complexes of niobocene

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Malcolm L. H. Green, J. Thomas James and Alexander N. Chernega

Abstract

The new compounds [Nb(η-C5H4R)(η-C5H4 R′)Cl(NNMe2)] (R = H or Me; R′ = H or Me), [Nb(η5-C5H4R)2(η 1-C5H4R)(NNMe2)] (R3 = Hx or Mey, x + y = 3), [Nb{CMe2(η5-C5H4 )(η1-C5H4)}(η5 -C5H5)(NNMe2)] and [Nb(η-C5H5)2(thf[hair space])(NNMe 2)][BPh4] (thf = tetrahydrofuran) have been prepared. The crystal structure of [Nb(η-C5H4Me)2Cl(NNMe2)] has been determined. A variable-temperature NMR study of [Nb(η5-C5H5)2(η 1-C5H5)(NNMe2)] reveals a fluxional interchange of the three cyclopentadienyl rings. This compound has been shown to react with the electrophiles SiMe3Cl, FeCl2·1.5thf, [NMe3H]Cl and [Nb(η-C5H5)Cl2(NNMe2)] to form in each case [Nb(η-C5H5)2Cl(NNMe2)]. A variable-temperature NMR study of [Nb{CMe2(η5-C5H4 )(η1-C5H4)}(η5 -C5H5)(NNMe2)] shows the presence of two interconvertible diastereomers. The bis- and tris-cyclopentadienyl compounds have been shown to undergo exchange of their cyclopentadienyl rings in solution with each other or Li(C5H4R). The compound [Nb(η-C5H5)(OBut)2 (NNMe2)] has also been shown to undergo a cyclopentadienyl ligand-exchange reaction.

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