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Treatment of an S-bridged penta-nuclear Ag I  3 Co III  2 complex, [Ag 3 {Co( L )} 2 ] 3+ [ L  3- = N(CH 2 NHCH 2 CH 2 S - ) 3 ], in which two tris-(thiol-ate)-type mononuclear Co III units ([Co( L )]) are bridged by three Ag I ions through S atoms, with iodo-methane (CH 3 I) gave a new Co III mononuclear complex, [Co( L Me 2 )] 2+ [ L Me 2  - = N(CH 2 NHCH 2 CH 2 S - )(CH 2 NHCH 2 CH 2 SCH 3 ) 2 ], systematic name: {2-[(bis{[2-(methylsulfanyl)ethyl]aminomethyl}aminomethyl)amino]ethanethiolato}cobalt(III) bis(hexafluoridophosphate). This cationic complex was crystallized with PF 6  - anions to form the title compound, [Co( L Me 2 )](PF 6 ) 2 . In the [Co( L Me 2 )] 2+ cation, two of three thiol-ate groups in [Co( L )] are methyl-ated while one thiol-ate group remains unreacted. Although a total of eight stereoisomers are possible for [Co( L Me 2 )] 2+ , only a pair of enanti-omers {Λ  RR  - and Δ  SS  -[Co( L Me 2 )] 2+ } are selectively formed. In the crystal, the complex cations and the PF- 6  - anions are connected through weak N-H⋯F, C-H⋯F and C-H⋯S hydrogen bonds into a three-dimensional structure. Two F atoms in one PF 6 anion are disordered over two sets of sites with refined occupancies of 0.61 (4) and 0.39 (4) and two F atoms in the other PF 6  - anion are disordered over two sets of sites with occupancies of 0.5.

acta crystallographica. section e, crystallographic communications

Synthesis and crystallographic characterization of a mononuclear cobalt(III) complex possessing both thiolate and thioether donors: reactivity of an thiolate-bridged pentanuclear Co<sub>2</sub>Ag<sub>3</sub> complex with iodomethane

Synthesis and crystallographic characterization of a mononuclear cobalt(III) complex possessing both thiolate and thioether donors: reactivity of an thiolate-bridged pentanuclear Co2Ag3 complex with iodomethane

Synthesis and crystallographic characterization of a mononuclear cobalt(III) complex possessing both thiolate and thioether donors: reactivity of an thiolate-bridged pentanuclear Co₂Ag₃ complex with iodomethane