Reactivity of Hg(II) ortho-cyano-aminothiophenolate coordination polymers [Hg{SC6H3XN(C≡N)}]n with cyclic aromatic amines, Ph3P = E (E = O, S) and [HgCl2(κ2-phen)

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We report reactions of Hg(II) ortho-cyano-aminothiophenolate coordination polymers, [Hg{SC6H3XN(C≡N)}]n, with donor ligands. Addition of cyclic aromatic amines, such as pyridine (L), leads to breakdown of the polymeric structure to give mononuclear four-coordinate complexes, [Hg{κ2 -SC6H3XN(C≡N)}L2], while 2,2’-bipy and 1,10-phen (L2) similarly afford mononuclear chelate complexes [Hg{κ2 -SC6H3XN(C≡N)}(κ2-L2)]. In contrast, Ph3P = E (E = O, S) form 1:1 complexes which, on the basis of related phosphine adducts, are formulated as binuclear [Hg{µ-SC6H3XN(C≡N)}(κ1-E = PPh3)]2. Reaction of [Hg{SC6H4N(C≡N)}]n with [HgCl2(κ2 -phen)] affords an adduct tentatively formulated as [Hg{κ2-SC6H4N(C≡N)}(µ-Cl)2Hg(κ2-phen)] in which the two chlorides bridge the Hg.Hg vector.