Functionalization of white phosphorus in the coordination sphere of transition metal complexes

A Reactive Niobium Phosphinidene P8 Cluster Obtained by Reductive Coupling of White Phosphorus

“…[2][3][4][5][6] Whereas degradation of P 4 into P 1 , P 2 , and P 3 ligands are common products of white phosphorus activation, aggregation into P x units, where x is greater than four, has been seen far less frequently.[5] An interesting case arises with the direct coupling of P 4 units to generate P 8 and P 12 ligands on mononuclear and polynuclear metal complexes.[7] Presented herein is a remarkable P 8 cluster ligand, which can be formed reproducibly in high yields under mild conditions, along with some initial exploration of its reaction chemistry and discussion of potential applications in generating organophosphorus derivatives.Previous work in our group has demonstrated the utility of three-coordinate, early-transition-metal fragments for the activation of white phosphorus. [8][9][10][11][12][13] The work described herein develops a new three-coordinate niobium platform using a previously synthesized 2-adamantylidene-(mesityl)enolate ligand, Mes[…”

“…Toward this end, some initial studies of the reactivity of 3 have been carried out. 3 (Et 2 O)] (5) forms as the reaction coproduct; however, it gets scavenged by the water that was added, and the final mixture contains 4, a small amount of oxo 5, and significant amounts of MesC(O)[ 2 Ad]. Despite these complications, 4 crystallizes from a benzene solution (slow evaporation) over the course of several days.…”

Catalytic Synthesis of Triaryl Phosphates from White Phosphorus

“…Examples of metals that have been found to activate P 4 include cobalt, rhodium and iridium. [5,14] Complexes formed from white phosphorus and iron compounds, such as pentaphosphaferrocene, have also been known for some time. [15] In addition to metal activation of P 4 , new allotropes of phosphorus stabilized by base (carbene) are investigated intensely as possible sources of unusual reactivity.…”

Formation of palladium phosphides in the reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus

“…On the one hand, the methods of activation of white phosphorus in the coordination sphere of the transition metal complexes were substantially developed, namely, the coordination chemistry of white phosphorus [1][2][3][4][5][6]. The structure of the formed phosphorus fragment is strongly influenced by the nature of the ligands in the coordination sphere of the transition metal.…”

“…The structure of the formed phosphorus fragment is strongly influenced by the nature of the ligands in the coordination sphere of the transition metal. Transition metal complexes having the molecule of Р 4 as a η 1 -ligand are stable only in the presence of bulky ligands in the coordination sphere of the metal [6], otherwise the splitting of the P-P bond occurs with subsequent recombination of small fragments into binuclear complexes or polyatomic aggregates [1][2][3][4], or hydrolytic oxidation in the presence of water [3,6]. The transition metal plays a role of a stabilizer of all phosphorus intermediates from the simplest phosphide anion to complex phosphorus oligomers Р n with up to 14 phosphorus atoms.…”