Recent advances in transition metal-mediated transformations of white phosphorus

Despite of the large interest by both industrial and academic chemists to develop a safe and environmentally acceptable process to functionalize white phosphorus, only few but significant steps have been developed in the last years. New experimental results and theoretical studies provide indeed a robust evidence that different metal complexes are really capable of mediating the formation of P-C bond starting from P4 and organic reagents and that even a catalytic process accomplishing the direct phosphorylation of alcoholos or orther organic substrates may be achieved via the intermediacy of a suitable metal complex. Nevertheless and in spite of the relevant findings achieved so far and of the impressive variety of metal complexes containing P atoms and polyphosphorus, Px, units which have been synthesized and characterized up to now, the original target of the direct (catalytic) phosphorylation of elemental phosphorus remains still unsolved. In this chapter the more recent results paving the way to the direct functionalization of white phosphorus, are presented and discussed

Structure and reactivity of transition metal substituted dichloroantimony and dichlorobismuth complexes

The dichloro Group 15 complexes [{Cpx(CO)2Fe}BiCl2] (Cpx = Cp, 5-C5H3tBu2{Cp}) 1a, b and [{Cp(CO)2Fe}SbCl2] 3 are prepared. The crystal structure determination of 1b and 3 shows a polymeric chlorine bridged structure for the bismuth complex 1b whereas for the antimony compound 3 a molecular structure with weak intermolecular chlorine bridges is found. The reaction of 1a or 3 with magnesium leads to the threefold transition-metal substituted complexes [(µ3-E){Fe(CO)2Cpx}3] ( 5: E = Bi, Cpx = Cp; 7: E = Sb, Cpx = Cp), whereas the analogous reaction of 1b results in the disubstituted bismuth chloro complex [{Cp(CO)2Fe}2BiCl] 6. Finally, the reaction of an equimolar mixture of 1a and 3 with magnesium yields the novel antimony-bridged compound [(µ3-Sb){Fe2(µ-CO)(CO)2Cp2}{Fe(CO)2Cp}] 8