Synthesis of zinc and cadmium O-alkyl thiocarbonate and dithiocarbonate complexes and a cationic zinc hydrosulfide complex

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• 作者：Nicholas G. Spiropulos^a ; Eric A. Standley^a ; Ian R. Shaw^a ; Benjamin L. Ingalls^a ; Bryan Diebels^a ; Sylvanna V. Krawczyk^b ; Benjamin F. Gherman^b ; Atta M. Arif^c ; Eric C. Brown^a ; ^{ericbrown3@boisestate.edu}
• 关键词：Heterocumulenes ; Zinc ; Cadmium ; Hydrosulfide ; Crystal structures ; DFT calculations
• 刊名：Inorganica Chimica Acta
• 出版年：2012
• 期刊代码：40_00201693
• 类别：ch
• 出版时间：15 May, 2012
• 卷：386
• 期：Complete
• 页码：83-92
• 文件大小：499 K

摘要

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^{鈭?/sup> (7) and ClO₄鈭?/sup> (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路6H₂O and Me₄NOH路5H₂O with COS in CH₃CN or (b) treating [((TPA)Zn)₂(渭-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.}