1,3,2-Dlheterophosphacyclanes in Rhodium(I) Complexes

The paper is concerned with rhodium(1) complexes of the type acacRh(CO)L, Rh(CO)ClL2, [Rh(CO)LCl]2, [acacRh(CO)[2L and [Rh(CO)LCl]n, where L: P are monodentate, P,N- and P,P-bidentate ligands including 1,3,2-diheterophospholane and phosphorinane cycles In our studies two synthetic approaches were used, viz. the interaction of tricoordinated phosphorus derivatives with the starting rhodium substrate proceeding via the associative mechanism and the reaction of pentacoordinated phosphorus derivatives (hydrospirophosphoranes) 31P, 1H, 13C NMR, IR spectroscopy as well as X-ray and chemical studies of rhodium-coordinated 1,3,2-diheterophos-phacyclanes were carried out. The properties of these organophosphorus ligands were shown to depend on the nature and configurational rigidity of the substituents X, Y, Z at the phosphorus atom. This is illustrated by the dependence of 1J(Rh, P) and ν (CO) on the size of the phosphorus ring and the position of the heteroatoms (O, N) in the ligand molecule.