Bis(trimethylsilyl)phosphinodithioformates, the phosphorus analogues of dithiocarbamates; X-ray structure of [Zr(cp)2(Cl)(η2-S2CPR2)] and its thermolysis product [{Zr(cp)2(µ-S)}2](cp =η-C5H5, R = SiMe3)

Abstract

Carbon disulphide inserts under ambient conditions into the Zr–P bond of [Zr(cp)₂(PR₂)X][cp =η-C₅H₅, R = SiMe₃] to yield [Zr(cp)₂(η²-S₂CPR₂)X][X = Cl (1a) or Me (1b)](having the novel phosphinodithioformato ligand, a phosphorus analogue of the dithiocarbamate), which upon heating affords [{Zr(cp)₂(µ-S)}₂](3){also obtained from S₈ and [Zr(cp)₂(PR₂)X](X = Me or PR₂)}; the [graphic omitted] and [graphic omitted] rings in (1a) and (3) are planar and the P environment in (1a) is pyramidal, with 〈Zr–S〉 2.686(8)(1a) and 2.483(3)Å(3) and SZrS′ 63.4(2)(1a) and 89.5(2)°(3).