title: Electronic structures of tris(dioxolene)chromium and tris(dithiolene)chromium complexes of the electron-transfer series [Cr(dioxolene)(3)](z) and [Cr(dithiolene)(3)](z) (z = 0, 1-, 2-, 3-). A combined experimental and density functional theoretical study.
abstract: From the reaction mixture of 3,6-di-tert-butylcatechol, H2[3,6L(cat)], [CrCl3(thf)3], and NEt3 in CH3CN in the presence of air, the neutral complex [CrIII(3,6L*(sq))3] (S = 0) (1) was isolated. Reduction of 1 with [Co(Cp)2] in CH2Cl2 yielded microcrystals of [Co(Cp)2][CrIII(3,6L*(sq))2(3,6L(cat))] (S = 1/2) (2) where (3,6L*(sq)(1-) is the pi-radical monoanionic o-semiquinonate of the catecholate dianion (3,6Lcat)(2-). Electrochemistry demonstrated that both species are members of the electron-transfer series [Cr(3,6LO,O)]z (z = 0, 1-, 2-, 3-). The corresponding tris(benzo-1,2-dithiolato)chromium complex [N(n-Bu)4][CrIII(3,5L*S,S)2(3,5LS,S)] (S = 1/2) (3) has also been isolated; (3,5LS,S)(2-) represents the closed-shell dianion 3,5-di-tert-butylbenzene-1,2-dithiolate(2-), and (3,5L*S,S)(1-) is its monoanionic pi radical. Complex 3 is a member of the electron-transfer series [Cr(3,5L(S,S))3]z (z = 0, 1-, 2-, 3-). It is shown by Cr K-edge and S K-edge X-ray absorption, UV-vis, and EPR spectroscopies, as well as X-ray crystallography, of 1 and 3 that the oxidation state of the central Cr ion in each member of both electron-transfer series remains the same (+III) and that all redox processes are ligand-based. These experimental results have been corroborated by broken symmetry density functional theoretical calculations by using the B3LYP functional.
authors: Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
authors: Ruta R
authors: RR
authors: Kapre
authors: Eberhard
authors: E
authors: Bothe
authors: Thomas
authors: T
authors: Weyhermüller
authors: Serena Debeer
authors: SD
authors: George
authors: Nicoleta
authors: N
authors: Muresan
authors: Karl
authors: K
authors: Wieghardt
mesh_terms: D002857:Chromium / Q000737:chemistry*; D004563:Electrochemistry; D004583:Electrons; D008024:Ligands; D008956:Models, Chemical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory; D013057:Spectrum Analysis
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; C524384:tris(dioxolene)chromium; C524385:tris(dithiolene)chromium; D002857:Chromium