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DOI: 10.1039/A608355B (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1953-1956

Reactions of α-lithiated phosphinimines with PhCN; the crystal structure of [[upper bond 1 start]K{N(H)C(Ph)C(H)P(Ph)2[double bond, length as m-dash]N[upper bond 1 end]SiMe 3}(tmen)]2 (tmen = Me2NCH2CH2NMe2)

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Peter B. Hitchcock, Michael F. Lappert and Zhong-Xia Wang

Abstract

Treatment of the α-lithiated phosphinimine [upper bond 1 start]Li{CH(R′)P(R)2[double bond, length as m-dash]N[upper bond 1 end]SiMe 3} with benzonitrile yielded (via a trimethylsilyl or hydrogen 1,3 C → N shift) the trimethylsilyliminophosphoranylenamidolithium complex [upper bond 1 start]Li{N(R′)C(Ph)C(H)P(R)2[double bond, length as m-dash]N[upper bond 1 end] SiMe3} (R = Me, R′ = SiMe3 1; R = Ph, R′ = SiMe3 2; or R = Ph, R′ = H 3). Complex 2 was transformed into the corresponding potassium complex 4 by an exchange reaction with KOBut. Crystallisation of 4 from hexane in the presence of Me2NCH2CH2NMe2 (tmen) gave the tmen adduct 5 and a trace of the partially hydrolysed product [[upper bond 1 start]K{N(H)C(Ph)C(H)P(Ph)2[double bond, length as m-dash]N[upper bond 1 end]SiMe 3}(tmen)]2 6, which was characterised by a single crystal X-ray diffraction study as a dinuclear complex with each of the two potassium atoms in a different co-ordination environment. Complex 1 or 2 was hydrolysed to form the neutral iminophosphoranylenamine [upper bond 1 start]N(SiMe3)C(Ph)C(H)P(R)2N(SiMe3) H[upper bond 1 end] 7 or 8, which showed (1H NMR spectroscopy) the presence of hydrogen bonds.

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