Reaction of [PtMe,(phen)] 1 (phen = 1.1 0-phenanthroline) with RE-ER gives the complexes [PtMe,(ER),(phen)] [2, ER = OH; 3, ER = OC(=O)Ph; 4, ER = SMe; 5, ER = SPh; 6, ER = SePh]. These contain predominantly isomer a in which the ER groups are trans but, in most cases, there is a minor product b in which the ER groups are cis; complexes 4-6 appear to be the first bis(thiolat0) or bis(seleno1ato) complexes of platinum( iv). The structures were determined by N M R spectroscopy and, in the case of complex 6a. by an X-ray structure determination [tetragonal, /4,/a, a = b = 13.918(2), c = 25.432(5) A, Z = 8, R = 0.0677, R' = 0.07051. In the reaction with PhSSPh, a sparingly soluble, black intermediate formulated as [{PtMei(phen)},( PhSSPh)] was formed.

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Model complexes for postulated intermediates in the preparatively important catalytic coupling of CO2 and epoxides to give cyclic carbonates are provided by the compounds 1 ( = bpy, phen; R = H, Ph, CH2OPh). They are formed upon reaction of [PtMe2( )] with epoxides under CO2 atmosphere. In principle, CO2 in the air should be sufficient.

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Modellkomplexe für postulierte Zwischenstufen der präparativ wichtigen katalytischen Kupplung von CO2 und Epoxiden zu cyclischen Carbonaten sind die Verbindungen 1 ( = bpy, phen; R = H, Ph, CH2OPh). Sie entstehen bei der Umsetzung von [PtMe2()] mit Epoxiden unter CO2‐Atmosphäre, wobei im Prinzip schon das CO2 der Luft genügt.