The synthesis and reactivity of some 2-ethyltetraphenoxydiphosphazane derivatives of rhodium

Abstract
Treatment of [{Rh(diene)Cl}2](diene = C8H12 or C7H8) with the ditertiary phosphite (PhO)2PN(Et)P(OPh)2(etdp) in benzene leads to successive replacement of the diene ligands and the formation of [Rh2(diene)(etdp)Cl2] and [{Rh(etdp)Cl}2]. The corresponding bromo- and iodo- derivatives [{Rh(etdp)X}2](X = Br or I) are produced analogously. Reactions of [{Rh(C8H12)Cl}2] with excess of etdp in ethanol or methanol in the presence of a suitable counter ion effects not only the displacement of the diene ligands but also the halogens as halide ions to afford [Rh(etdp)2][A](A = BPh4 or SbF6). Carbon monoxide reacts reversibly with [Rh(etdp)2]+ and [Rh(C8H12)(etdp)]+ obtained by treatment of [Rh(C8H12)(solvent)x]+ with etdp, to yield [Rh(etdp)2(CO)]+ and [Rh(C8H12)(etdp)(CO)]+ respectively. Reaction of [Rh(etdp)2]+ with HBr and Br2 gives trans-[Rh(etdp)2H(Br)]+ and [Rh(etdp)2Br2]+ respectively, although the former degrades to [Rh(etdp)2]+ in solution.

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