Synthesis, structure and solution NMR properties of (Ph 4P)[M(SeC{O}Tol) 3], M = Zn, Cd and Hg

Abstract

Metal selenocarboxylate salts (PPh 4)[M(SeC{O}Tol) 3] (M = Zn (1), Cd (2) and Hg (3); Tol = C 6H 4-p-CH 3) have been synthesized by reacting Zn(NO 3) 2·6H 2O, Cd(NO 3) 2·4H 2O or HgCl 2 with Na +TolC{O}Se - and PPh 4Cl in the ratio of 1:4:1. The structures of these compounds were determined by single-crystal X-ray diffraction methods. The crystal structures contain discrete cations and anions. In the each anion, the metal center is bound to three TolC{O}Se ligands, primarily through Se, though some long M⋯O interactions also occur. NMR spectra ( 113Cd, 199Hg and 77Se, as appropriate) are reported for solutions of [M(SeC{O}Tol) 3] -, and of [M(SeC{O}Tol) 3] --[M(SC{O}Ph) 3] - mixtures (M = Zn- Hg), in CH 2Cl 2 at reduced temperatures. In addition, ESI-MS data have been obtained for [M(SeC{O}Tol) 3] --[M(SC{O}Ph) 3] - mixtures (M = Zn-Hg) in acetone and in CH 2Cl 2. The NMR and ESI-MS studies show that the complexes [M(SeC{O}Tol) n(SC{O}Ph) 3-n] - (n = 3-0) persist in solution.