Rhodium(I) Complexes with a η-Fluorenyl--phosphanylphosphorane Ligand.

The first example of a -phosphanylphosphorane, Flu═PCy-PCy (; Flu = 9-fluorenyl), has been easily prepared by P-phosphination of lithiated 9-dicyclohexylphosphinofluorene (FluPCy, ) with chlorodicyclohexylphosphane. constitutes a new type of P(III)-P(V) organophosphorus compound, a σλ-σλ species that is stable under an inert atmosphere in the solid state. The reaction of with [Rh(diene)]BR causes metalation of the benzylic carbon (C9) of fluorene, giving κ-C,P complexes in which fluorene is coordinated in the η form.

Rhodium and ruthenium complexes of methylene-bridged, -stereogenic, unsymmetrical diphosphanes.

Enantiopure -stereogenic methylphosphane-boranes ()-P(BH)PhArMe (; Ar = 1-naphthyl (NpMe), and 2-biphenylyl (BiphMe)) have been used to prepare diphosphanes of the type ArPhPCHPR (R = Ph, iPr or Bu; ). The ligands have been reacted with [Rh(COD)]BF to furnish the corresponding six monochelated [Rh(COD)()]BF organometallic compounds (RhArR) or, depending on the reaction conditions, the bis(chelated) coordination compound [Rh()]BF as a mixture of and isomers. The crystal structure of -[Rh()]BF was obtained.