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Reaction of allylamine with 1 equiv. of Ph2PCl in the presence of NEt3, proceeds in THF to give (allylamino)phosphane 1. 1 has been coordinated as a monodentate P ligand with Au, Pd, Pt, Ru, Rh, Ir and as a bidentate P,allyl ligand to Pt. Reaction of KOtBu with [PtCl2{Ph2PNH(C3H5)}2] in methanol gives [Pt{Ph2PNH(C3H8O)}2]. The X‐ray structures of 1.Se and four demonstrative monodentate complexes all reveal intramolecular N–H···Cl hydrogen bonding. The structure of [Pt{Ph2PNH(C3H8O)}2] consists of an N–H···O hydrogen‐bonded dimer in the solid state. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

While thermolysis of thiocarbonyl-stabilised phosphonium ylides generally results in extrusion of Ph(3)PS to give alkynes, those with a P=CH function instead undergo a novel P to S transfer of a phenyl group to give (Z)-configured 1-phosphino-2-sulfenylalkenes of interest as bidentate ligands.

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