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Complexes of a dianionic bis(diphosphinomethanide) with lithium, sodium, potassium and zirconium. Effect of substitution on the Schlenk dimerisation of vinylidene phosphines

Lookup NU author(s): Dr Keith Izod, Emeritus Professor William McFarlane, Brent Tyson, Emeritus Professor Bill CleggORCiD, Dr Ross Harrington



The vinylidene phosphine (Prn2P)2C=CH 2 (1) undergoes Schlenk dimerisation on treatment with an excess of any of the alkali metals Li, Na or K to give the butane-1,4-diide complexes [(L)M{(Prn2P)2CCH2}]2 [(L)M = (THF)2Li (6), (THF)3Na (7b), (DME)2K (8b)], after recrystallisation. Whereas the reaction between the analogous phenyl derivative (Ph2P)2C=CH2 and K results in cleavage of a P-C bond, 1 reacts smoothly with K to give 8, with no evidence for P-C cleavage. Compound 6 is an excellent ligand transfer reagent: metathesis reactions between either 6 or its phenyl analogue [(THF)2Li{(Ph 2P)2CCH2}]2 (2) and two equivalents of Cp2ZrCl2 in THF give the corresponding dinuclear zirconocene derivatives [Cp2Zr(Cl){(R2P) 2CCH2}]2 in good yields [R = Ph (11), Pr n (12)]. Compounds 6, 7b, 8b, 11 and 12 have been characterised by multi-element NMR spectroscopy and, where possible, by elemental analysis; compounds 6, 7b, 11 and 12 have additionally been characterised by X-ray crystallography.

Publication metadata

Author(s): Izod K, McFarlane W, Tyson BV, Clegg W, Harrington RW

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2004

Issue: 23

Pages: 4074-4078

Date deposited: 09/07/2010

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry


DOI: 10.1039/b413970d


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