Bond Stretching and Redox Behavior in Coinage Metal Complexes of the Dichalcogenide Dianions [(SPh2P)2CEEC(PPh2S)2]2− (E=S, Se): Diradical Character of the Dinuclear Copper(I) Complex (E=S)
Konu, J., Chivers, T., & Tuononen, H. (2011). Bond Stretching and Redox Behavior in Coinage Metal Complexes of the Dichalcogenide Dianions [(SPh2P)2CEEC(PPh2S)2]2− (E=S, Se): Diradical Character of the Dinuclear Copper(I) Complex (E=S). Chemistry - A European Journal, 17(42), 11844-11856. https://doi.org/10.1002/chem.201100891
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Chemistry - A European JournalDate
2011Copyright
© 2011 Wiley-VCH Verlag GmbH & Co.This is a final draft version of an article whose final and definitive form has been published by WIley. Published in this repository with the kind permission of the publisher.
The metathetical reactions of a) [Li(tmeda)]2[(S)C(PPh2S)2] (Li2⋅3 c) with CuCl2 and b) [Li(tmeda)]2[(SPh2P)2CSSC(PPh2S)2] (Li2⋅4 c) with two equivalents of CuCl both afford the binuclear CuI complex {Cu2[(SPh2P)2CSSC(PPh2S)2]} (5 c). The elongated (C)S[BOND]S(C) bond (ca. 2.54 and 2.72 Å) of the dianionic ligand observed in the solid-state structure of 5 c indicate the presence of diradical character as supported by theoretical analyses. The treatment of [Li(tmeda)]2[(SPh2P)2CSeSeC(PPh2S)2] (Li2⋅4 b) and Li2⋅4 c with AgOSO2CF3 produce the analogous AgI derivatives, {Ag2[(SPh2P)2CEEC(PPh2S)2]} (6 b, E=Se; 6 c, E=S), respectively. The diselenide complex 6 b exhibits notably weaker Ag[BOND]Se(C) bonds than the corresponding contacts in the CuI congeners, and the 31P NMR data suggest a possible isomerization in solution. In contrast to the metathesis observed for CuI and AgI reagents, the reactions of Li2⋅4 b and Li2⋅4 c with Au(CO)Cl involve a redox process in which the dimeric dichalcogenide ligands are reduced to the corresponding monomeric dianions, [(E)C(PPh2S)2]2− (3 b, E=Se; 3 c, E=S), and one of the gold centers is oxidized to generate the mixed-valent AuI/AuIII complexes, {Au[(E)C(PPh2S)2]}2 (7 b, E=Se; 7 c, E=S), with relatively strong aurophilic AuI⋅⋅⋅AuIII interactions. The new compounds 5 c, 6 b,c and 7 b,c are characterized in solution by NMR spectroscopy and in the solid state by X-ray crystallography (5 c, 6 b, 7 b and 7 c) and by Raman spectroscopy (5 c and 6 c). The UV-visible spectra of coinage metal complexes of the type 5, 6 and 7 are discussed in the light of results from theoretical analyses using time-dependent density functional theory.
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