Solid-State 113Cd NMR Studies of Several Cadmium-Sulfur Complexes. Shielding Tensor-Structure Correlations

Joan Sola, Pilar González-Duarte, Isidre Casals, Teresa Alsina, Jesús Sanz, Isabel Sobrados, Angel Alvarez-Larena, Joan Francesc Piniella, Xavier Solans

Research output: Contribution to journalArticleResearchpeer-review

24 Citations (Scopus)

Abstract

113Cd CP/MAS-NMR spectra have been recorded for seven cadmium complexes including [Et4N]2[Cd2-(SC6H11)6] (1), [Me4N][Cd(S2CSC6H11)3] (2), [Cd(SC5H9NHMe)2][ClO4]2 (3), [Cd{S(CH2)3NHMe2}X2] (X = Cl (4), Br (5)), [Cd4{S(CH2)2NMe2}4Br4] (6), and [Cd4{S(CH2)2NMe2}6Cl2] (7). Compounds 1 and 2 have been structurally characterized by X-ray crystallography. The former consists of discrete dinuclear [Cd2(SR)6]2− units containing CdS4 tetrahedral sites. The same coordination geometry is also present in polymeric complexes 3–5 with CdS4 (3) and CdS2X2 (X = Cl (4), Br (5)) environments. Two different cadmium sites coexist in complexes 6 and 7, both formed by discrete tetranuclear molecules with Cd4S4 rings. Coordination around cadmium is tetrahedral in CdS2Br2 and CdS2N2⋯Br2 sites of complex 6, a severe distortion toward octahedral geometry being present in the second site. In complex 7 there are an octahedral CdS2N2Cl2 environment and a highly distorted CdS3N⋯Cl center with a planar CdS3 moiety. The structure of 2 includes mononuclear [Cd(SS)3]− anions, where the CdS6 coordination unit is distorted from a regular octahedron toward a trigonal prism. The shielding tensor, isotropic chemical shift (σiso), chemical shielding anisotropy (Δσ), and asymmetry parameter (η) have been determined for all the sites. An orientation of the principal elements of the 113Cd shielding tensor is proposed for each cadmium environment. The magnitude of the tensor principal components in terms of the structural features around the cadmium atom is discussed as well as the variations of tensor elements in sites of close symmetry as a function of changes in the stereochemistry. © 1993, American Chemical Society. All rights reserved.
Original languageEnglish
Pages (from-to)10018-10028
JournalJournal of the American Chemical Society
Volume115
Issue number22
DOIs
Publication statusPublished - 1 Nov 1993

Fingerprint Dive into the research topics of 'Solid-State <sup>113</sup>Cd NMR Studies of Several Cadmium-Sulfur Complexes. Shielding Tensor-Structure Correlations'. Together they form a unique fingerprint.

Cite this