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Monomeric alkali metal complexes of a sterically demanding, donor-functionalised secondary phosphide ligand

Lookup NU author(s): Emeritus Professor Bill CleggORCiD, Dr Simon DohertyORCiD, Dr Keith Izod, Paul O'Shaughnessy, Dr Joanne Sheffield


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The novel sterically demanding, amino-functionalised secondary phosphine (2-Me2NCH2C6H4)RPH [R = CH(SiMe3)2] was synthesized by the reaction of RPCl2 with [Li{C6H4CH2NMe2-2}], followed by reduction with LiAlH4. The compound is readily metallated with BunLi to yield the lithium phosphide [Li{PR(C6H4CH2NMe2-2)}(THF) 2] 1·2THF, in which the ligand binds to Li through both its N and P. Metathesis between 1 and NaOBut or KOBut yielded the sodium and potassium phosphides [M{PR(C6H4CH2NMe2-2)}] (M = Na 2 or K 3), respectively. Compound 2 crystallises as the monomeric adduct [Na{PR(C6H4CH2NMe2-2)}(tmen)], in which the formally four-co-ordinate Na exhibits a short contact with one of the ipso-carbons of the phosphide ligand. Compound 3 crystallises in the presence of pmdien as the mononuclear adduct [K{PR(C6H4CH2NMe2-2)}-(pmdien)] in which the potassium centre is only five-co-ordinate, although again showing a short K ⋯ Cipso contact. The compounds have been characterised by multinuclear NMR spectroscopy, and 1-3 by X-ray crystallography.

Publication metadata

Author(s): Clegg W, Doherty S, Izod K, Kagerer H, O'Shaughnessy P, Sheffield JM

Publication type: Article

Publication status: Published

Journal: Journal of the Chemical Society - Dalton Transactions

Year: 1999

Issue: 11

Pages: 1825-1829

Print publication date: 07/06/1999

ISSN (print): 0300-9246

ISSN (electronic): 1364-5447

Publisher: Royal Society of Chemistry


DOI: 10.1039/a900869a


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