摘要
The unprecedented nickel(III) thiolate [Ni III (OR)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 ) - [R = Ph (1), Me (3)] containing the terminal Ni III -OR bond, characterized by UV-vis, electron paramagnetic resonance, cyclic voltammetry, and single-crystal X-ray diffraction, were isolated from the reaction of [Ni III (Cl)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] _ with 3 equiv of [Na][OPh] in tetrahydrofuran (THF)-CH 3 CN and the reaction of complex 1 with 1 equiv of [Bu 4 N][OMe] in THF-CH 3 OH, respectively. Interestingly, the addition of complex 1 into the THF-CH 3 OH solution of [Me 4 N][OH] also yielded complex 3. In contrast to the inertness of complex [Ni III (Cl)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] - toward 1 equiv of [Na][OPh], the addition of 1 equiv of [Na][OMe] into a THF-CH 3 CN solution of [Ni III (Cl)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] - yielded the known [Ni III (CH 2 CN)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] - (4). At 77 K, complexes 1 and 3 exhibit a rhombic signal with g values of 2.31, 2.09, and 2.00 and of 2.28, 2.04, and 2.00, respectively, the characteristic g values of the known trigonal-bipyramidal Ni III [Ni III (L)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] - (L = SePh, SEt, Cl) complexes. Compared to complexes [Ni III (EPh)(P(C 6 H 3 -3-SiMe 3 -2-S) 3 )] - [E = S (2), Se] dominated by one intense absorption band at 592 and 590 nm, respectively, the electronic spectrum of complex 1 coordinated by the less electron-donating phenoxide ligand displays a red shift to 603 nm. In a comparison of the Ni III -OMe bond length of 1.885(2) Å found in complex 3, the longer Ni III -OPh bond distance of 1.910(3) Å found in complex 1 may be attributed to the absence of σ and π donation from the [OPh]-coordinated ligand to the Ni III center. © 2008 American Chemical Society.