Fluorophosphines chemistry

Recent Progress in the Chemistry of Fluorophosphines John F. Nixon... 

Electron Spin Resonance of Transition Metal Complexes B. A. Goodman and J. B. Raynor Recent Progress in the Chemistry of Fluorophosphines John F. Nixon... 

Organic derivatives of phosphorus trichloride—i.e., chlorophosphines of the types RPC12 or R2PC1—had never been fluorinated. We assumed the hitherto unknown fluorophosphines to be possibly interesting ligands in coordination chemistry. Such expectations were supported by earlier observations of Chatt (5, 6) and Wilkinson (32), who found that the parent compound phosphorus trifluoride as a ligand in certain coordination compounds with platinum or nickel behaved very much like carbon monoxide. 

The comparatively simple method of preparation of tetrakis (trifluorophos-phine)nickel-(0) encouraged some scouting experiments on its still unexplored chemistry. Whereas the compound is hydrolytically remarkably stable, it was found to react readily with amines and ammonia with complete aminolysis of the phosphorus-fluorine bonds. Very typical of tetrakis(trifluorophosphine) nickel-(0) and similar fluorophosphine and chlorophosphine complexes of zerovalent nickel is the rapid decomposition with precipitation of elemental nickel by aqueous alkali hydroxide. 

By far the most extensively used synthetic route involves the technique of reductive fluorophosphination developed by T. Kruck and co-workers (174), who have made many important contributions to the development of the field of transition metal-PF3 chemistry. In this method the appropriate metal halide is heated in an autoclave (usually copper-lined) with reducing agents, e.g., copper or zinc, in the presence of PF3(50-500 atm) (method C). For example,... 

A theoretical study of the intermediates involved in the formation of phospha-propyne from pyrolysis of vinylphosphirane has led to a new route to phospha-alkynes. Thus, pyrolysis of trimethylsilyl(l-phosphiranyl)diazomethane has yielded MeaSiC = P, via an intermediate 1-phosphiranylmethylene . Regioselec-tivity in the [3 + 2] cycloaddition reaction between phosphaethyne and diazomethane has been studied by theoretical techniques , and further examples of reactions of this type described . Cycloaddition of phospha-alkynes with silylenes has also been reported. The primary phosphine 324 has been isolated from the addition of diethylphosphite to t-butylphosphaethyne. The chemistry of phospha-alkyne cyclotetramer systems has been reviewed and the first examples of platinum(II) complexes of such cage systems described. Aspects of the reactivity of coordinated phospha-alkynes have received further study, and a remarkable metal-mediated double reduction of t-butylphosphaethyne to the complexed fluorophosphine 325 described Phosphorus-carbon-aluminium cage structures have been isolated from the reactions of kinetically stable phospha-alkynes with trialkylaluminium compounds and new phosphaborane systems have been obtained from the reactions of phospha-alkynes with polyhedral boranes . Further studies of wo-phospha-alkyne coordination chemistry have appeared . The reactivity of the ion 326 has been explored. ... 

Fluorophosphines are tervalent phosphorus compounds containing phosphorus-fluorine bonds and they often show markedly different chemical behavior compared with other halogenophosphines. This article is mainly concerned with recent advances in the chemistry of derivatives of PF 3 of the type PF3 X , with particular reference to (a) synthesis of new structural types, (6) the role of fluorophosphines as ligands, particularly in transition metal complexes, and (c) nuclear magnetic resonance (NMR) studies. 

Since fluorophosphines form part of a general review of phosphorus fluorides (282), and there is an excellent account of transition metal-trifluorophosphine complexes (152), the present article is not intended to be comprehensive, but rather to highlight some of the more recent developments in this expanding area of inorganic chemistry. 

---