Stepwise degradation of trifluoromethyl platinum(II) compounds

The action of moisture on the homoleptic organoplatinum(II) compound [NBu(4)](2)[Pt(CF(3))(4)] (1) gives rise to the carbonyl derivative [NBu(4)][Pt(CF(3))(3)(CO)] (2), which is itself moisture stable. However, treatment of compound 2 with HCl(aq) results in the formation of [NBu(4)][cis-Pt(CF(3))(2)Cl(CO)] (3), which undergoes degradation of an additional CF(3) group by further treatment with HCl(aq) in large excess, affording [NBu(4)][cis-Pt(CF(3))Cl(2)(CO)] (4). The carbonyl derivatives 2-4 are fairly stable species, in which the CO ligand, however, can be readily extruded by reaction with trimethylamine N-oxide (ONMe(3)). Thus, compound 2 reacts with ONMe(3) in the presence of a number of neutral or anionic ligands affording a series of singly or doubly charged derivatives with the general formulae [NBu(4)][Pt(CF(3))(3)(L)] [L = CNtBu (5), PPh(3) (6), P(o-tolyl)(3) (7), tht (8; tht = tetrahydrothiophene)] and [NBu(4)](2)[Pt(CF(3))(3)X] [X = Cl (9), Br (10), I (11)], respectively. Compound 2 also reacts with ONMe(3) and pyridin-2-thiol (C(5)H(5)NS) giving rise to the five-membered metallacyclic derivative [NBu(4)][Pt(CF(3))(2)(CF(2)NC(5)H(4)S-κC,κS)] (12), which can be viewed as a difluorocarbene species stabilized by intramolecular base coordination. On the other hand, treatment of compound 3 with ONMe(3) in the presence of C(5)H(5)NS yields the four-membered metallacyclic compound [NBu(4)][Pt(CF(3))(2)(NC(5)H(4)S-κN,κS)] (13). The geometries of the metallacycles in compounds 12 and 13 are compared. In the absence of any additional ligand, compound 3 undergoes dimerization producing the dinuclear species [NBu(4)](2)[{Pt(CF(3))(2)}(2)(μ-Cl)(2)] (14). Halide abstraction in the latter compound with AgClO(4) in THF yields the solvento compound cis-[Pt(CF(3))(2)(thf)(2)] (15). The highly labile character of the THF ligands in compound 15 makes this species a convenient synthon of the "cis-Pt(CF(3))(2)" unit.