Halogen and pseudohalogen substitution of some adamantanoid chalcogenate clusters [(μ-EPh)6(MEPh)4]2− using methylmercury and triphenyltin derivatives. A multinuclear nuclear magnetic resonance study

Multinuclear nmr (1H, 77Se, 111/113Cd, 119Sn, 199Hg, as appropriate) has been used to study Y−−EPh− exchange in Me2CO or MeCN between RnM′Y (RnM′ = Ph3Sn or MeHg; Y = Cl, Br, I, NCO, or NCS) and the adamantane-like anions [(μ-EPh)6(MEPh)4]2− (E = S, M = Zn, Cd, or Co; E = Se, M = Zn or Cd), as their tetraalkylammonium salts. Quantitative terminal substitution of the clusters occurs in most cases, giving [(μ-EPh)6(MEPh)4 − x(MY)x]2−(x = 1–4). However, reaction is incomplete for M = Cd, E = S or Se, RnM′Y = Ph3SnNCO or Ph3SnNCS and for M = Zn or Co, E = S, RnM′Y = MeHgI. Differences in the extents of reaction for Ph3SnY and MeHgY are consistent with the position of equilibrium in MeHgY:Ph3SnEPh mixtures.Group interchange provides a convenient alternative synthesis of the known halogen-substituted clusters [(μ-EPh)6(MY)4]2−(M = Zn or Cd, Y = Cl, Br, or I; M = Co, Y = Cl), and the first syntheses of [(μ-SPh)6(CoY)4]2− (Y = Br or I) and various pseudohalogen-substituted adamantanoid anions. The nuclei used for full direct nmr characterization of the new clusters in solution were: 77Se and 113Cd for [(μ-SePh)6(CdSePh)4 − x(CdY)x]2− (x = 1–4; Y = NCO or NCS); 77Se for [(μ-SePh)6(ZnSePh)4 − x(ZnY)x]2− (x = 1–4, Y = NCO or NCS); 113Cd for [(μ-SPh)6(CdSPh)4 − x(CdY)x]2−(x = 1–4; Y = NCO or NCS); 1H for [(μ-SPh)6(CoY)4]2− (Y = Br, I, NCO, or NCS). The first solution 1H nmr spectrum of [(μ-SPh)6(CoCl)4]2− is also reported.