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Homoleptic coordination of the neutral diphosphines Me2P(CH2)2PMe2 and o-C6H4(PMe2)2 to the hard Li(+) and Na(+) cations is achieved using Li[Al{OC(CF3)3}4] and Na[B{3,5-(CF3)2-C6H3}4] as 'naked' cation sources. Crystallographic, solid state and solution multinuclear NMR studies confirm distorted octahedral coordination solely via three chelating diphosphines in these unique species.

Unique Group 1 cations stabilised by homoleptic neutral phosphine coordination