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Synthesis and Crystal Structure of Tellurium(II) bis(2‐methoxycarbonylethanethiolate): A Novel Coordination Mode of Tellurium
Author(s) -
Fleischer Holger,
Hennig Sandra,
Schollmeyer Dieter
Publication year - 2003
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200300193
Subject(s) - tellurium , intramolecular force , chemistry , crystallography , molecule , ab initio , ab initio quantum chemistry methods , atom (system on chip) , coordination complex , nuclear magnetic resonance spectroscopy , acceptor , crystal structure , stereochemistry , inorganic chemistry , metal , organic chemistry , physics , computer science , embedded system , condensed matter physics
The tellurium(II) dithiolates Te[SCH 2 CH 2 C(O)OCH 3 ] 2 , ( 1 ), Te[SCH 2 CH 2 CH 2 SC(O)CH 3 ] 2 , ( 2 ), and Te[SCH 2 CH 2 CH 2 CH 2 SC(O)CH 3 ] 2 , ( 3 ) were synthesized from Te(S t Bu) 2 and the corresponding thiol. All compounds are sensitive toward higher temperatures and light and decompose to elemental tellurium and the disulfide. In the solid state, the Te atom of 1 exhibits the novel Te(S 2 Te 2 ) coordination mode. Additionally to the two Te—S bonds, each Te atom forms two long Te···Te contacts to neighboring molecules, leading to a coordination number of four and a distorted sawhorse configuration. No intramolecular Te···O interactions are present in the solid state, in accordance with ab initio calculations (MP2/ecp‐basis) for the isolated molecule. 125 Te NMR shifts of all compounds lay within a narrow range and close to the respective shift of other Te(SCH 2 R) 2 compounds. VT 125 Te NMR spectra gave no hint to donor acceptor interactions in solution for any of the compounds and thus corroborate results from IR‐spectroscopy, ab initio geometry optimizations, and thermochemical calculations.