116862-80-7Relevant articles and documents
Thiolato-technetium complexes. 1. Synthesis and characterization of bis(tertiary diphosphine)technetium(III) complexes containing methanethiolato ligands. Single-crystal structural analyses of trans -[TcIII(SCH3)2(DMPE)2]CF 3SO3 and trans-[TcIII(SCH3)2(DEPE)2 ...
Konno, Takumi,Heeg, Mary Jane,Deutsch, Edward
, p. 4113 - 4121 (2008/10/08)
Full title: Thiolato-technetium complexes. 1. Synthesis and characterization of bis(tertiary diphosphine)technetium(III) complexes containing methanethiolato ligands. Single-crystal structural analyses of trans -[TcIII(SCH3)2(DMPE)2]CF 3SO3 and trans-[TcIII(SCH3)2(DEPE)2]PF 6, where DMPE = 1,2-bis(dimethylphosphino)ethane and DEPE = 1,2-bis(diethylphosphino)ethane. The Tc(III) methanethiolato complexes trans-[Tc(SCH3)2D2]+, where D is either 1,2-bis(dimethylphosphino)ethane (DMPE) or 1,2-bis(diethylphosphino)ethane (DEPE), have been synthesized and characterized. Preparation of these complexes from [TcV(O)(OH)D2]2+ utilizes excess NaSCH3 as reductant and ligand. The X-ray crystal structures of both title complexes are examined. trans- [Tc(SCH3)2(DMPE)2]CF3SO3, chemical formula TcS3P4F3O3C15H 38, crystallizes in the triclinic space group P1 with a = 7.9615 (13) ?, b = 9.3019 (7) ?, c = 18.5029 (16) ?, α = 88.093 (7)°, β = 89.686 (11)°, γ = 88.188 (11)°, V = 1368.8 (3) ?3, and Z = 2. The final weighted R value is 0.032. The coordination complex is approximately octahedral with average Tc-P = 2.428 ? (range 2.422 (2)-2.434 (2) ?), Tc-S = 2.300 ? (range 2.298 (2)-2.302 (2) ?), and S-C = 1.842 ? (range 1.837 (7)-1.847 (7) ?). trans-[Tc(SCH3)2(DEPE)2]PF6, chemical formula TcS2P5F6C22H54, crystallizes in the monoclinic space group P21/c with a = 11.0724 (13) ?, b = 11.2450 (11) ?, c = 14.1331 (14) ?, β = 107.957 (8)°, V = 1674.0 (3) ?3, and Z = 2. The final weighted R value is 0.022. This complex is also nearly octahedral with average Tc-P = 2.449 ? (range 2.4399 (8)-2.4584 (7) ?), Tc-S = 2.3025 (5) ?, and S-C = 1.821 (4) ?. In both structures the Tc atom occupies an inversion center. The visible spectra of these trans-[Tc(SCH3)2D2]+ complexes in acetonitrile show sulfur-to-technetium charge-transfer bands at 16 810 and 28 490 cm-1 for D = DMPE and at 16 610 and 28 830 cm-1 for D = DEPE. Cyclic voltammetric measurements in N,N-dimethylformamide show two reversible reduction couples corresponding to Tc(III/II) and Tc(II/I) at -0.550 and -1.72 V vs Ag/AgCl for D = DMPE and -0.554 and -1.81 V vs Ag/AgCl for D = DEPE. The absorption spectra and cyclic voltammograms are compared with those of other trans- [TcD2X2]+ complexes with X = Cl, Br, -NCS and are discussed in terms of the relative strengths of the σ and π interactions between Tc and the ligating S and P atoms.
