Abstract
Addition reactions between ERH2(E = P or As; R = Ph, CH2CH2CN, Bu or C6H2But3-2,4,6) and (Ph2P)2CCH2 or (Ph2P)2CCHR′(R′= H or Me) yield the triphosphines (Ph2P)2CHCHR′ERH and the pentaphosphines [(Ph2P)2CHCH2]2ER and (Ph2P)2CHCH(Me)P(Ph)CH2CH(PPh2)2. The two- and three-bond 31P–31P nuclear spin-spin coupling constants in these vary substantially with the bulk of substituents on or near phosphorus, probably as a result of conformation differences. The structures of (Ph2P)2CHCH2PHPh, (Ph2P)2PCHCH2PH(C6H2But3-2,4,6) and [(Ph2P)2CHCH2]2PPh have been determined by X-ray diffraction and suggest that each of these species adopts a conformation in solution that is very similar to that found in the solid state.
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