Aspects of the chemistry of some phosphorus halides and pseudohalides

The preparation of pseudohalogeno derivatives of the simple phosphorus(V) species PC1(_4)(^+), PC1(_5) and PC1(_6)(^-) has been attempted. In the case of the tetrachlorophosphonium ion only azido-derivatives are observable in normal organic solvents, cyano and thiocyanato derivatives being more stable in liquid halogen media. Isolation of these compounds was not possible. Molecular derivatives based on PC1(_5) seem to be particularly unstable and are only readily observable under forcing conditions for cyanide. The derivatives of the hexachlorophosphate ion are all observable, PX(_6)(^-) being readily formed for X = N(_3), NCS, NCO and OCN although these and the intermediate species are all unstable. The series of cyanides PC1(_6-n)(CN)(_n)(^-) (0 < n < 3) have been isolated as solids and fully characterised, and the presence of isomers for n = 2 and 3 has been clearly established. The six-coordinate fluorochlorophosphates PF(_3)Cl(_3)(^-), PF(_2)C1(_4)(^-) and PFC1(_5)(^-) have been isolated as pure tetraalkylammonium salts and the reactions of these anions studied with respect to substitution by pseudohalides. The observation of PF(_6-n)X(_n)(^-) (X = pseudohalogen) has been carried out by ligand exchange between PF(_6)(^-) and PX(_6)(^-) (where known) or PX(_3) and attempts have been made to isolate compounds, where feasible, by other reactions such as the addition of pseudohalide ions to PF(_5).The use of pairwise interactions has proved invaluable in assigning formulae in the tetrahedral systems, and in both assigning formulae and identifying specific isomers in many of the six-coordinate systems. The substitution patterns in the six-coordinate systems can be rationalised in terms of a simple steric model, or on the basis of ligand field theory for the cyanides. Other six-coordinate systems have been studied with respect to substitution by azide and several new species have been identified.