Effect of peripheral donor substituents on the binding modes of phosphinomethanide ligands. Synthesis and crystal structures of alkali metal derivatives of an O-functionalised phosphinomethanide ligand
Izod, Keith; Young, Jonathan; Clegg, William; Harrington, Ross W.; Izod Keith; Department of Chemistry, School of Natural Sciences, Bedson Building, University of Newcastle; Young Jonathan; Department of Chemistry, School of Natural Sciences, Bedson Building, University of Newcastle; Clegg William; Department of Chemistry, School of Natural Sciences, Bedson Building, University of Newcastle; Harrington Ross W.; Department of Chemistry, School of Natural Sciences, Bedson Building, University of Newcastle
Журнал:
Dalton Transactions
Дата:
2005
Аннотация:
The O-functionalised tertiary phosphine {(Me3Si)2CH}P(C6H4-2-CH2OMe)2 (9) is accessible via the reaction of {(Me3Si)2CH}PCl2 with two equivalents of in situ generated 2-LiC6H4CH2OMe. Phosphine 9 is readily deprotonated by Bu<sup>n</sup>Li to give the lithium phosphinomethanide [[{(Me3Si)2C}P(C6H4-2-CH2OMe)2]Li] (13), which undergoes metathesis reactions with the alkoxides MOR [M = Na, K, R = Bu<sup>t</sup>; M = Rb, R = 2-ethylhexyl] to give the heavier alkali metal phosphinomethanides [[{(Me3Si)2C}P(C6H4-2-CH2OMe)2]M]n in good yields [M = Na (14), n = 2; M = K (15), Rb (16), n = â ]. Compounds 9, [{(Me3Si)2CH}P(C6H4-2-CH2OMe)2LiBr]2 (10), and 14â 16 have been studied by X-ray crystallography; in the solid state 14 adopts a dimeric structure, whereas 15 and 16 crystallise as one-dimensional polymers.
181.8Кб