期刊
INORGANICA CHIMICA ACTA
卷 386, 期 -, 页码 83-92出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2012.01.040
关键词
Heterocumulenes; Zinc; Cadmium; Hydrosulfide; Crystal structures; DFT calculations
资金
- Boise State University
- NIH from National Center for Research Resources [P20 RR0116454]
- SURE from the College of Natural Sciences and Mathematics at California State University, Sacramento
- NSF [CRIF/MU-0639251, CCLI-0737128, CHE-0923535]
Treatment of Zn(II) and Cd(II) hydroxide complexes of the tris(2-pyridylmethyl) amine (TPA) ligand with COS or CS2 in protic solvents (MeOH or EtOH) resulted in [(TPA) Zn-SC(S)OCH3]ClO4 (1), [(TPA)Zn-SC(O)OCH3]BF4 (2), [(TPA) Zn-SC(O)OCH3]ClO4 (3), [(TPA)Zn-SC(O)OCH2CH3]BF4 (4), [(TPA)Cd-SC(S)OCH3]ClO4 (5) and [(TPA)Cd-SC(O)OCH3]ClO4 (6). The molecular structures of 1, 2, 5 and 6 were determined by X-ray crystallography. Complexes 2, 3 and 4, unlike 1, 5 and 6, are easily hydrolyzed upon treatment with water in CH3CN to give zinc hydrosulfide complexes of the form [(TPA) Zn-SH] X (X = BF4 (7) and ClO4 (8)), as evidenced by spectroscopic methods and the crystal structure of 7. These complexes may be prepared more directly by (a) reacting equimolar amounts of TPA, Zn(ClO4)(2)center dot 6H(2)O and Me4NOH center dot 5H(2)O with COS in CH3CN or (b) treating [((TPA) Zn)(2)(mu-OH)(2)](ClO4)(2) with H2S. Moreover, reactivity and density functional theory computational studies comparing the cationic hydrosulfide complexes 7 and 8 with the neutral zinc hydrosulfide complexes supported by tris(pyrazolyl) borate ligands have been conducted and subtle differences between the two types of hydrosulfide complexes have been determined. (C) 2012 Elsevier B. V. All rights reserved.
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