Preparative and structural studies on [NiII(L)(N(CH 2CH2S)2(CH2CH2SH))] 0/1 (L = PEt3, SePh)

A Ni(II)-mixed-chalcogenolate carbonyl complex, [PPN][Ni(CO)(SePh) 2(S-p-C6H4-Cl)] (1) was obtained from the treatment of [CpNi(μ-S-p-C6H4-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(CH2CH2S)2(CH2CH 2SH))] (2) and [Ni(PEt3)(N(CH2CH2S) 2(CH2CH2SH))] (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 (VSH = 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-C6H4S)2(o-C6H4SH)]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(CH2CH2S)2(CH2CH 2SH)]2- ligand, precluding the pendant thiol from pointing a direction to the nickel and thiolato sulfur.