Heterobimetallische Komplexe von Titan(IV)Quecksilber(II) und Platin(II)Quecksilber(II)

The reaction of [Ti](CCR1)2 {[Ti]=(η5-C5H4SiMe3)2Ti; 1a: R1=C6H5, 1b: R1=SiMe3} with several mercury(II) compounds HgX2 (2a: X=CN, 2b: X=OCN, 2c: X=OAc, 2d: X=SCN, 2e: X=O2CCF3, 2f: X=Cl, 2g: X=I) and Hg(R2)(R3) (6a: R2=C6H5, R3=CF3; 6b: R2=R3=C6H5) is described. Depending on the nature of X, R2 and R3 different products are formed: Reaction of 1a with Hg(CN)2 (2a) and Hg(CF3)(C6H5) (6a) produces the heterobimetallic titanium(IV)mercury(II) complexes {[Ti](CCC6H5)2}Hg(CN)2 (3a) and {[Ti](CCC6H5)2}Hg(CF3)(C6H5) (7), while the reaction of 1b with Hg(OCN)2 (2b) or Hg(OAc)2 (2c) affords non-characterizable products. However, when 2d–2g are used in the reaction with 1b, a redox process takes place, producing [Ti]X2 (4a: X=NCS, 4b: X=O2CCF3, 4c: X=Cl, 4d: X=I), Me3SiCCCCSiMe3 (5) and Hg(0). As intermediate the formation of the organometallic π-tweezer complex {[Ti](CCSiMe3)2}HgX2 (3d: X=SCN, 3e: X=O2CCF3, 3f: X=Cl, 3g: X=I) is postulated. A similar reaction behavior is found, when 1a or 1b is reacted with PdCl2, PtCl2 or AuCl3, respectively. An access to heterobimetallic platinum(II)mercury(II) complexes of type {(bipy′)Pt(CCC6H5)2}HgX2 (bipy′=4,4′-dimethyl-2,2′-bipyridine; 9a: X=Cl, 9b: X=I) is given by the reaction of (bipy′)Pt(CCC6H5)2 (8) with stoichiometric amounts of HgX2 (2f: X=Cl, 2g: X=I). All complexes were characterized by elemental analysis and by spectroscopy (IR, 1H-, 13C{1H}-NMR, MS).