Issue 10, 2017

Cadmium complexes bearing Me2N^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 CH3 groups 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.

Graphical abstract: Cadmium complexes bearing Me2N^E^O− (E = S, Se) organochalcogenoalkoxides and their zinc and mercury analogues

Supplementary files

Article information

Article type
Paper
Submitted
23 Jan 2017
Accepted
13 Feb 2017
First published
15 Feb 2017

Dalton Trans., 2017,46, 3179-3191

Cadmium complexes bearing Me2N^E^O (E = S, Se) organochalcogenoalkoxides and their zinc and mercury analogues

A. Pop, C. Bellini, R. Şuteu, V. Dorcet, T. Roisnel, J. Carpentier, A. Silvestru and Y. Sarazin, Dalton Trans., 2017, 46, 3179 DOI: 10.1039/C7DT00279C

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