Bi- and trinuclear cationic complexes involving bonds between mercury and five-coordinate platinum(II). Molecular structure of [{Pt(2,9-dimethyl-1,10-phenanthroline)-(Z-MeO2CCH = CHCO2Me)(H2O)}2 Hg](BF4)2
摘要:
Three cationic five-coordinate platinum(II) complexes bearing alkylmercury fragments as ''ligands'' have been isolated. The complexes of general formula [Pt(HgR)H2O)dmphen)(ZR' O2CCH=CHCO(2)R')] (BF4) (dmphen=2,9-dimethyl-1,10-phenanthroline; R, R(t)=Me; R=Me, R(t) =(t)Bu; R=(t)Bu, R(t)=Me) are stabilized by the factors operating in related neutral species. Two of the new complexes slowly demercuriatez in solution, affording the mononuclear complexes [Pt(Me)H2O)(dmphen(ZR' O2CCH=CHCO(2)R(t))](BF4) (R(t)=Me or (t)Bu). When R=(t)Bu, a slow redistribution reaction is observed, yielding the trinuclear cluster [{Pt(dmphen)(Z-MeO(2)CCH=CHCO(2)Me)H2O)}Hg-2](BF4)(2). The structure of this complex has been determined by X-ray analysis.
Trigonal-bipyramidal co-ordinatively saturated platinum(II) olefin complexes bearing an organomercury fragment in axial position
摘要:
The reactions of organomercury halides HgR'(Cl) (R' = Me, Et, Bu(t) or Ph) with complexes of the type [Pt(dmphen){(Z)-RO2CCH = CHCO2R}] (dmphen = 2,9-dimethyl-1,10-phenanthroline; R = Me, Et or Bu(t)) have been studied. The dmphen ligand with suitable 'in-plane' steric hindrance stabilizes five-co-ordinate adducts of general formula [PtCl(HgR')(dmphen){(Z)-ROCCH-CHCO2R}] when R' = alkyl. An influence of the nature of the Hg-bound hydrocarbyl group on the reaction course is observed. Thus, a cluster containing the Pt-Hg-Pt sequence was obtained when R' = Ph or Cl. The molecular structure of [PtCl(HgMe)(dmphen){(Z)-MeO2CCH=CHCO2Me}] (space group P2(1)/c; a = 13.079(2), b =1 3.167(2), c = 15.495(3) angstrom and beta = 94.18(2)-degrees] reveals a large trans influence of the organomercury fragment.