Heterobimetallic complexes of titanium(IV)-mercury(II) and platinum(II)-mercury(II)

The reaction of [Ti](C=CR1)(2) ([Ti] = (eta(5)-C5H4SiMe3)(2)Ti; 1a: R-1 = C 6H5, 1b: R-1 = 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 = 1) and Hg(R-2)(R-3) (6a: R-2 = C6H5, R-3 = CF3; 6b: R-2 = R-3 = C6H5) is de scribed. Depending on the nature of X, R-2 and R-3 different products are f ormed: Reaction of 1a with Hg(CN)(2) (2a) and Hg(CF3)(C6H5) (6a) produces t he 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 pro ducts. However, when 2d-2g are used in the reaction with 1b, a redox proces s takes place, producing [Ti]X-2 (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 pi-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, res pectively. An access to heterobimetallic platinum(II)-mercury(II) complexes of type ((bipy')Pt(C=CC6H5)(2)) HgX2 (bipy' = 4,4'-dimethyl-2,2'-bipyridin e; 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 compl exes were characterized by elemental analysis and by spectroscopy (IR, H-1- , C-13(H-1)-NMR, MS).