Isomerism and conformation of (N-silyl)bis(diphenylphosphino)amines and bis(N-silyl)diphenylphosphinoamines

Hubert Schmidbaur, Sybille Lauteschläger, Frank H. Köhler

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Lithium bis(diphenylphosphino)amide (2) reacts with chlorotriorgano- and dichlorodiorganosilanes to form either N-silylbis(diphenylphosphino)amides (3) or the isomeric P-diphenylphosphinodiphenylphosphine(silylimides) (4), or an equilibrium mixture of both. The nature of the product depends strongly on the nature of the substituents attached to silicon. 29Si and 31P NMR spectroscopy were used to differentiate between the two structures. In N,N-bis(trimethylsilyl)aminodiphenylphosphine the two silyl groups were found by NMR spectroscopy to be non-equivalent at low temperature in solution, and this is attributed to hindered rotation about the PN bond, with an in-plane (Si2NP) orientation of the lone pair of electrons at phosphorus as the ground state. The reaction of 2 with (CH3)2PCl does not yield triphosphinoamine species; instead, a P-phosphinophosphinimine (5) is obtained, which is closely related to the silyl analogues of formula 4.

Original languageEnglish
Pages (from-to)173-180
Number of pages8
JournalJournal of Organometallic Chemistry
Issue number1-3
StatePublished - 21 Aug 1984
Externally publishedYes


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