Preparative and Structural Studies on [Ni~Ⅱ(L)(N(CH_2CH_2S)_2(CH_2CH_2SH))]~(0/1-) (L = PEt_3, SePh): A Thiol in the Secondary Coordination Sphere

摘要

A Ni(Ⅱ)-mixed-chalcogenolate carbonyl complex, [PPN][Ni(CO)(SePh)_2(S-p-C_6H_4-Cl)] (1) was obtained from the treatment of [CpNi(μ-S-p-C_6H_4-Cl)]_2 and fac-[PPN][Fe(CO)_3(SePh)_3]. Using 1 as a precursor, two four-coordinated square planar Ni(Ⅱ)-chalcogenolate/chalcogenol complexes, [PPN][Ni-(SePh)(N(CH_2CH_2S)_2(CH_2CH_2SH))] (2) and [Ni(PEt_3)(N(CH_2CH_2S)_2(CH_2CH_2SH))] (4) containing the thiol in the secondary coordination sphere have been synthesized and identified by single-crystal X-ray diffraction. Analyses of structural data and vibrational energy (v_(SH) = 2431 cm~(-1) for 4) reveal that the pendant thiol in complexes 2 and 4, respectively do not form intramolecular interaction with the nickel and thiolato sulfur. Compared to previously reported analogues coordinated by [P(o-C_6H_4S)_2(o-C_6H_4SH)]~(2-) ligand (Chen, C.-H.; Lee, G.-H.; Liaw, W.-F. Inorg. Chem. 2006, 45, 2307), the lack of intramolecular interaction in complexes 2 and 4 may be attributed to the rotatable C-S and C-C bonds of [N(CH_2CH_2S)_2(CH_2CH_2SH)]~(2-) ligand, precluding the pendant thiol from pointing a direction to the nickel and thiolato sulfur.