title: Dimerization processes of square planar [PtII(tbpy)(dithiolato*)]+ radicals.
abstract: The preparation and structural characterization of the neutral, square planar complexes [PtII(tbpy)(A)] (1), [PtII(tbpy)(B)] (2), and [PtII(PPh3)2(B)] (3) have been accomplished, where (tbpy) = 4,4'-di-tert-butylpyridine, (A)2- = 3,6-bis(trimethylsilyl)-1,2-benzenedithiolate(2-), and (B)2- = 1,2-bis(4-tert-butylphenyl)ethylene-1,2-dithiolate(2-) and (A*)1- and (B*)1- represent the corresponding monoanionic radicals. Electrochemical and chemical one-electron oxidation of 1 and 2 in CH2Cl2 solution affords the monomeric monocations [PtII(tbpy)(A*)]+ (1a) and [PtII(tbpy)(B*)]+ (2a), both of which possess an S = 1/2 ground state. The corresponding spin doublet monocationic dimers [PtII2(tbpy)2(A)(A*)]+ (1b) and [PtII2(tbpy)2(B)(B*)]+ (2b) were electrochemically generated in solution (50% oxidation) and identified by X-band EPR spectroscopy. Complete one-electron oxidation of 1 and 2 yielded the diamagnetic dimers [PtII2(tbpy)2(A*)2]2+ (1c) and [PtII2(tbpy)2(B*)2]2+ (2c) which are in equilibrium with the corresponding paramagnetic monomers 1a and 2a in solution. The crystal structure of [PtII2(tbpy)2(B*)2](PF6)2.3CH2Cl2 (2c) revealed a centrosymmetric, lateral dimer whose bridging part is a PtII2(mu2-S)2 rhomb; the metal ions possess a square based pyramidal geometry. Solid-state sulfur K-edge X-ray absorption spectra of 1, 2, 2a, 2c, and [PtII(B*)2]0 (4) have been recorded, which clearly show that a sulfur-centered radical (B*)1- is present in 2a, 2c, and 4. The absence of ligand-based radicals in 1 and 2 is also clearly established. One-electron oxidation of [Pt(PPh3)2(B)] (3) afforded only the spin doublet species [PtII(PPh3)2(B*)]+ (3a); no dimer formation was detected. Synthesis and crystal structure of square planar [PtII(B*)2]0.thf are also reported.
authors.affiliation: Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
authors.forename: József Sándor
authors.initials: JS
authors.lastname: Pap
authors.forename: Flávio Luiz
authors.initials: FL
authors.lastname: Benedito
authors.forename: Eberhard
authors.initials: E
authors.lastname: Bothe
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.forename: Serena DeBeer
authors.initials: SD
authors.lastname: George
authors.forename: Thomas
authors.initials: T
authors.lastname: Weyhermüller
authors.forename: Karl
authors.initials: K
authors.lastname: Wieghardt
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry; D007202:Indicators and Reagents; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009944:Organoplatinum Compounds / Q000138:chemical synthesis*; D010984:Platinum / Q000737:chemistry
chemical_list: D005609:Free Radicals; D007202:Indicators and Reagents; D008024:Ligands; D009944:Organoplatinum Compounds; C521230:Pt(II)(4,4'-di-tert-butylpyridine)(3,6-bis(trimethylsilyl)-1,2-benzenedithiolate); D010984:Platinum