Reactions of the anionic platinum complexes (NBu(4))[Pt(PPh(3))(C(6)F(5))(2)(OCOCH(3))] (1) and (NBu(4))(2)[Pt(C(6)F(5))(3)(S)] (S = methanol or acetone) with Tl(I) salts afford the heterometallic neutral cis-[(C(6)F(5))(2)(PPh(3))Pt(&mgr;(2)-OOCCH(3))Tl] (2) and the dimeric dianionic (NBu(4))(2)[{(C(6)F(5))(3)Pt}(2){(&mgr;(2)-O,&mgr;(3)-O'CCH(3))Tl}(2)] (3). Both complexes display Pt-Tl bonds with bond lengths of 2.994(1) Å and 2.884(1) Å, respectively, the latter being the shortest Pt-Tl(I) distance reported so far. The structure of both compounds has been established by X-ray studies.
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