title: Cadmium complexes bearingMe2N^E^O-(E = S, Se) organochalcogenoalkoxides and their zinc and mercury analogues.
abstract: Heteroleptic zinc and cadmium complexes of the type [{Me2N^E^OR2}M-Nu]n(M = Zn, Cd; E = S, Se; R = CH3, CF3; Nu = N(SiMe3)2, I, Cl; n = 1-2) were prepared by reacting the alcohol proteo-ligands {Me2N^E^OR2}H with [M(N(SiMe3)2)2] (M = Zn, Cd) or [XMN(SiMe3)2] (M = Zn, X = Cl; M = Cd, X = I) in an equimolar ratio. These group 12 metal complexes were characterised in solution by multinuclear NMR spectroscopy and their solid-state structures were determined by X-ray diffractometry. The ligands {Me2N^E^O(CH3)2}-bearing CH3groups in α position to the alkoxide behave as κ2-O,E-bidentate moieties (E = S, Se) and form centro-symmetric dinuclear O-bridged heteroleptic alkoxo-amido complexes both with zinc and cadmium, with four-coordinate metal centres resting in tetrahedral environments. By contrast, complexes supported by the CF3-substituted {Me2N^E^O(CF3)2}-crystallise as tetrahedral mononuclear species, with tridentate κ3-N,O,E-coordinated ligands. These structural differences resulting from changes in the ligand skeleton and in the electron-donating properties of the alkoxide were also observed in solution. Attempts to prepare congeneric heteroleptic mercury complexes from [Hg(N(SiMe3)2)2] unexpectedly only afforded homoleptic bis(alkoxide)s such as [{Me2N^S^O(CF3)2}2Hg]. Owing to the strong Hg-C bond, treatment of [PhHgN(SiMe3)2] with {Me2N^S^O(CF3)2}H afforded the heteroleptic, T-shaped [{Me2N^S^O(CF3)2}HgPh] mercuric alkoxide upon elimination of hexamethyldisilazane. [{Me2N^S^O(CF3)2}2Hg] and [{Me2N^S^O(CF3)2}HgPh] constitute very rare examples of structurally characterised mercuric alkoxides.
authors.affiliation: Supramolecular Organic and Organometallic Chemistry Centre, Chemistry Department, Faculty of Chemistry and Chemical Engineering, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania. ancas@chem.ubbcluj.ro.
authors.forename: Alexandra
authors.initials: A
authors.lastname: Pop
authors.affiliation: Université de Rennes 1, CNRS, Institut des Sciences Chimiques de Rennes, UMR 6226, Campus de Beaulieu, F-35042 Rennes Cedex, France. yann.sarazin@univ-rennes1.fr.
authors.forename: Clément
authors.initials: C
authors.lastname: Bellini
authors.affiliation: Supramolecular Organic and Organometallic Chemistry Centre, Chemistry Department, Faculty of Chemistry and Chemical Engineering, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania. ancas@chem.ubbcluj.ro.
authors.forename: Răzvan
authors.initials: R
authors.lastname: Şuteu
authors.affiliation: Université de Rennes 1, CNRS, Institut des Sciences Chimiques de Rennes, UMR 6226, Campus de Beaulieu, F-35042 Rennes Cedex, France. yann.sarazin@univ-rennes1.fr.
authors.forename: Vincent
authors.initials: V
authors.lastname: Dorcet
authors.affiliation: Université de Rennes 1, CNRS, Institut des Sciences Chimiques de Rennes, UMR 6226, Campus de Beaulieu, F-35042 Rennes Cedex, France. yann.sarazin@univ-rennes1.fr.
authors.forename: Thierry
authors.initials: T
authors.lastname: Roisnel
authors.affiliation: Université de Rennes 1, CNRS, Institut des Sciences Chimiques de Rennes, UMR 6226, Campus de Beaulieu, F-35042 Rennes Cedex, France. yann.sarazin@univ-rennes1.fr.
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Carpentier
authors.affiliation: Supramolecular Organic and Organometallic Chemistry Centre, Chemistry Department, Faculty of Chemistry and Chemical Engineering, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania. ancas@chem.ubbcluj.ro.
authors.forename: Anca
authors.initials: A
authors.lastname: Silvestru
authors.affiliation: Université de Rennes 1, CNRS, Institut des Sciences Chimiques de Rennes, UMR 6226, Campus de Beaulieu, F-35042 Rennes Cedex, France. yann.sarazin@univ-rennes1.fr.
authors.forename: Yann
authors.identifier: http://orcid.org/0000-0003-1121-0292
authors.initials: Y
authors.lastname: Sarazin