摘要
The reaction of MnBr 2 and [PPN] 2 [S,S-C 6 H 3 -R] (1:2 molar ratio) in THF yielded [(THF)Mn(S,S-C 6 H 3 -R) 2 ] - [R = H (1a), Me (1b); THF = tetrahydrofuran]. Formation of the dimeric [Mn(S,S-C 6 H 3 -R) 2 ] 2 2- [R = H (2a), Me (2b)] was presumed to compensate for the electron-deficient Mn III core via two thiolate bridges upon dissolution of complexes 1a and 1b in CH 2 Cl 2 . Complex 2a displays antiferromagnetic coupling interaction between two Mn III centers (J = -52 cm -1 ), with the effective magnetic moment (μ eff ) increasing from 0.85 μ B at 2.0 K to 4.86 μ B at 300 K. The dianionic manganese(II) thiolate complexes [Mn(S,S-C 6 H 3 -R) 2 ] 2- [R = H (3a), Me (3b)] were isolated upon the addition of [BH 4 ] - into complexes 1a and 1b or complexes 2a and 2b, respectively. The anionic mononuclear {Mn(NO)} 5 thiolatonitrosylmanganese complexes [(NO)Mn(S,S-C 6 H 3 -R) 2 ] - [R = H (4a), Me (4b)] were obtained from the reaction of NO(g) with the anionic complexes 1a and 1b, respectively, and the subsequent reduction of complexes 4a and 4b yielded the mononuclear (Mn(NO)} 6 [(NO)Mn(S,S-C 6 H 3 -R) 2 ] 2- [R = H (5a), Me (5b)]. X-ray structural data, magnetic susceptibility measurement, and magnetic fitting results imply that the electronic structure of complex 4a is best described as a resonance hybrid of [(L)(L)Mn III NO • )] - and [(L)(L • )Mn III (NO - )] - (L = 1,2-benzenedithiolate) electronic arrangements in a square-pyramidal ligand field. The lower IR v NO stretching frequency of complex 5a, compared to that of complex 4a (shifting from 1729 cm -1 in 4a to 1651 cm -1 in 5a), supports that one-electron reduction occurs in the {(L)(L • )Mn III } core upon reduction of complex 4a. © 2008 American Chemical Society.