摘要:
Coupling of dichloroplatinum complexes with ethyne or butadiyne, catalyzed by CuI in the presence of Et2NH, leads to complexes of the types [Pt(C=CH)(2)L-2] (L-2 = dppe (1), dppp (2); L = PEt3 (3)) and [Pt(C=CC=CH)(2)L-2] (L-2 = dppp (4), dcpe (5); L = PEt3 (6)). Attempts to produce tetraplatinum species with ethynyl edges proved unsuccessful, but further coupling of the butadiynylplatinum complexes with [PtCl2L2] produces the neutral molecular squares [Pt(mu-Cequivalent toCCequivalent toC)(2)L-2](4) (L-2 = dppp (7), dcpe (8); L = PEt3 (9)). This two-step approach allows the synthesis of the unsymmetrical complexes [Pt-2(mu-Cequivalent toCCequivalent toC)(2)(PEt3)(2)L-2] (L-2 = dppp (10); dcpe (11)). The molecular structure of 7 reveals that each square has a puckered, butterfly-like structure. These pack in a face-to-face manner, generating series of channels that accommodate several solvent molecules. Coupling of trans-[Pt(Cequivalent toCCequivalent toC)(2)(PEt3)(2)] (6b) with [PtCl2L2] (L-2 = dcpe, dppp) leads to complexes assigned as neutral octaplatinum derivatives. The nitrogen-containing complexes [Pt(C=CC5H4N)(2)(dppp)] (14) and [Pt(Cequivalent toCC(6)H(4)CN)(2)(dppp)] (15) react with AgNO3 to produce Pt4Ag4 adducts.