title: Heterocyclic thionates as a new class of bridging ligands in oxo-centered triangular cyclopentadienylchromium(III) complexes.
abstract: The interactions of the benzothiazolate complex, CpCr(CO)(2)(SCSN(C(6)H(4))) (2), and the tetrazole thiolate complex, CpCr(CO)(3)(eta(1)-SCN(4)Ph) (3), with controlled amounts of Me(3)OBF(4) and (MeO)(2)SO(2), respectively, produced the corresponding mu(3)-oxo trinuclear thionate-bridged complexes, [Cp(3)Cr(3)(mu(2)-OH)(mu(3)-O)(mu(2)-eta(2)-SCSN(C(6)H(4)))(2)](5)BF(4) (45%) and [Cp(3)Cr(3)(mu(2)-OH)(mu(3)-O)(mu(2)-eta(2)-SCN(4)Ph)(2)](9)(MeOSO(3)) (53%), together with their respective free dimethylated thiolate ligands, [MeSCSNMe(C(6)H(4))](4)BF(4) and (Me(2)SCN(4)Ph)(8)MeOSO(3). The reaction of 3 with Me(3)OBF(4) resulted in the isolation of a binuclear complex, [Cp(2)Cr(2)(mu-OH)(mu-eta(2)-SCN(4)Ph)(2)](7)BF(4) (43%), and (8)BF(4) (27%). The reaction of the thiopyridine complex, CpCr(CO)(2)(SPy) (4), with I(2) also produced a similar mu(3)-oxo complex 10 (31%), together with CpCrI(2)(THF) (11) and the disulfide (SPy)(2). Similar reactions with 2 and 3 and I(2) yielded species 5 and 7, together with 11 and disulfides derived from their respective ligands. Cyclic voltammograms recorded in solutions of 5 and 9 indicated that the compounds could be reduced and oxidized at very similar potentials. An EPR spectrum characteristic of a compound with axial symmetry was obtained for 9 at 7 K. Single-crystal X-ray diffraction analyses confirmed that species 7 is dinuclear, whereas 5 and 9 are structural trinuclear analogues, each containing a mu(3)-oxo central core.
authors: Department of Chemistry, National University of Singapore, Kent Ridge, Singapore 117543.
authors: Victor Wee Lin
authors: VW
authors: Ng
authors: Seah Ling
authors: SL
authors: Kuan
authors: Weng Kee
authors: WK
authors: Leong
authors: Lip Lin
authors: LL
authors: Koh
authors: Geok Kheng
authors: GK
authors: Tan
authors: Lai Yoong
authors: LY
authors: Goh
authors: Richard D
authors: RD
authors: Webster
mesh_terms: D002857:Chromium / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003517:Cyclopentanes / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000145:classification; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D013457:Sulfur Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000145:classification
chemical_list: D003517:Cyclopentanes; D006571:Heterocyclic Compounds; D008024:Ligands; D009942:Organometallic Compounds; D013457:Sulfur Compounds; D002857:Chromium; D010100:Oxygen