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Preparative and Structural Studies on [Ni II (L)(N(CH 2 CH 2 S) 2 (CH 2 CH 2 SH))] 0/1−1 (L = PEt 3 , SePh): A Thiol in the Secondary Coordination Sphere
Author(s) -
Chen ChienHong,
Yen ShihYing,
Huang TzuTing,
Lee GeneHsiang,
Kuo TingShen,
Lee ChienMing
Publication year - 2013
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201200558
Subject(s) - chemistry , intramolecular force , thiol , ligand (biochemistry) , nickel , stereochemistry , crystallography , crystal structure , organic chemistry , biochemistry , receptor
A Ni(II)‐mixed‐chalcogenolate carbonyl complex, [PPN][Ni(CO)(SePh) 2 (S‐ p ‐C 6 H 4 ‐Cl)] ( 1 ) was obtained from the treatment of [CpNi(μ‐S‐ p ‐C 6 H 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 2 CH 2 S) 2 (CH 2 CH 2 SH))] ( 2 ) and [Ni(PEt 3 )(N(CH 2 CH 2 S) 2 (CH 2 CH 2 SH))] ( 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 (ν 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 6 H 4 S) 2 ( o ‐C 6 H 4 SH)] 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 2 CH 2 S) 2 (CH 2 CH 2 SH)] 2− ligand, precluding the pendant thiol from pointing a direction to the nickel and thiolato sulfur.