Organoplatinum compounds VII - Trimethylplatinum fluoride [(CH3)(3)PtF](4), the missing link in organoplatinum cluster chemistry: its synthesis, crystal structure and a comparison to the crystal structure of [(CH3)(3)PtOH](4)

摘要

The structural chemistry of organoplatinum clusters [Me3PtX](4) (X = halide) has been completed with the synthesis and X-ray investigation of [Me3PtF](4) (1) and its structural comparison to the well-known hydroxide [Me3PtOH](4) (2), all members of the 'organoplatinum cubane' family. Compound 1, long withstanding its attempted synthesis, has been obtained by the reaction of [Me3PtI](4) with XeF2 as a mild fluorinating agent in form of colourless crystals: space group I(4) over bar 3 m, Z = 2, a = 10.0878(7) Angstrom, R-1 = 0.0242, wR(2) = 0.0563. In order to discriminate 1 from its possible hydrolysis product, viz. [Me3PtOH](4) (2), the latter was also synthesised according to literature procedures and re-investigated by X-ray crystallography: colourless crystals, space group I(4) over bar 3 m, Z = 2, a = 10.1400(10) Angstrom, R-1 = 0.0238, wR(2) = 0.0586. NMR spectroscopic, mass spectrometric and, in part, IR data are reported for 1 and 2. A crystalline solid obtained from equimolar chloroform solutions of both 1 and 2 did not reveal any new structural features, e.g. lattice parameters. From this mixture one might have expected a possible formation of strong hydrogen bonds of the type Me3Pt-F ... H-O-PtMe3. (C) 1998 Elsevier Science S.A. All rights reserved. [References: 12]