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• W2803953886 abstract "Abstract Complexes of the type (PPh3)2M(μ-SEt)2E(SEt)2 (M = Cu, Ag; E = Al, Ga, In) are effective and versatile molecular precursors for bimetallic and mixed MES2 chalcopyrite nanomaterials. In solution at room temperature, these compounds exhibit spectroscopic characteristics inconsistent with their cyclic solid state structures, and variable temperature NMR investigations in this report show that this discrepancy is a result of rapid exchange of thiolate groups between bridging and terminal positions. These experiments show that the exchange is unimolecular and does not involve phosphine dissociation or free thiol. Exchange rates are not strongly affected by thiolate electronic properties or the identity of E, but are significantly slower for more sterically demanding phosphine and thiolate ligands. Data are consistent with a simple turnstyle exchange mechanism involving dissociation of one bridging thiolate ligand from M, although crossover studies suggest that full ionic dissociation (into [(PPh3)2M][E(SEt)4]) is also facile, and that dissociation into neutral fragments (PPh3)2MSEt + E(SEt)3 may proceed at higher temperatures. Additional investigation of the solution state thermolyses of the same complexes demonstrates that the processes above do not correlate to their decomposition behavior, as thermal sensitivity is most strongly effected by thiolate electronic properties, and likely depends most strongly on cleavage of C S bonds." @default.
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• W2803953886 date "2018-08-01" @default.
• W2803953886 modified "2023-09-24" @default.
• W2803953886 title "Solution state fluxionality and thermolysis reactions of bimetallic single source precursors for I-III-VI chalcopyrite materials" @default.
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• W2803953886 doi "https://doi.org/10.1016/j.ica.2018.05.021" @default.
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