title: Square planar bis{3,6-bis(trimethylsilyl)benzene-1,2-dithiolato}metal complexes of Cr(II), Co(III), and Rh(II): an experimental and density functional theoretical study.
abstract: The three square planar complexes [N(n-Bu)(4)](2)[Cr(II)L(2)] x 4 CH(3)CN (S = 2; 1), [N(n-Bu)(4)][Co(III)L(2)] (S = 1; 3), and [N(n-Bu)(4)](2)[Rh(II)L(2)] x 4 CH(3)CN (S = 1/2; 4) have been prepared and structurally characterized by X-ray crystallography (L(2-) represents the 3,6-bis(trimethylsilyl)benzene-1,2-dithiolate(2-)). Aerial oxidation of CH(2)Cl(2) solutions of 1 produced purple crystals of [N(n-Bu)(4)][Cr(V)OL(2)] x 2 CH(2)Cl(2) (S = 1/2; 2), the structure of which has also been determined by X-ray crystallography. The electro- and magnetochemistry of all species has been studied. Their electronic structures have been experimentally investigated by recording their electronic and EPR spectra; solid-state temperature-dependent magnetic susceptibility measurements have been performed. Density functional theoretical calculations at the ZORA-B3LYP level have been carried out for all four species in order to obtain a better understanding of the electronic structure of the square planar complexes and the one-electron reduced [Rh(I)L(2)](3-) species. The reactivity of the latter with CH(3)I has been studied, and two products have been identified: cis-[Rh(III)I(2)(L'')(L')] and cis-[Rh(III)(CH(3))(I)(L'')(L')] where (L')(-) represents the S-methylated monoanion of L(2-) and (L'')(0) is the neutral, twice-S-methylated form of (L)(2-).
authors.affiliation: Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
authors.forename: Flávio Luiz
authors.initials: FL
authors.lastname: Benedito
authors.forename: Taras
authors.initials: T
authors.lastname: Petrenko
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Thomas
authors.initials: T
authors.lastname: Weyhermüller
authors.forename: Karl
authors.initials: K
authors.lastname: Wieghardt
mesh_terms: D002857:Chromium / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D012238:Rhodium / Q000737:chemistry*; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D014297:Trimethylsilyl Compounds; C547044:bis(3,6-bis(trimethylsilyl)benzene-1,2-dithiolato); D002857:Chromium; D003035:Cobalt; D012238:Rhodium