Synthesis and Molecular Structure of the Dihydrobis(thioxotriazolinyl)borato Complexes of Zinc(II), Bismuth(III), and Nickel(II). M···H-B Interaction Studied by Ab Initio Calculations
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- 作者：Roberto Cammi ; Maurizio Lanfranchi ; Luciano Marchiò ; Clara Mora ; Cristiano Paiola ; and Maria Angela Pellinghelli
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：March 10, 2003
- 年：2003
- 卷：42
- 期：5
- 页码：1769 - 1778
- 全文大小：197K
- 年卷期：v.42,no.5(March 10, 2003)
- ISSN：1520-510X
文摘
Reacting the heterocycle 5-thioxo-1,4-dihydro-4-ethyl-3-methyl-1,2,4-triazole (thioxotriazoline) with sodium tetrahydroborate in the molar ratio of ~2:1 at 130 
C provides the new ligand dihydrobis(thioxotriazolinyl)borato, [BtEt,Me]-,as its sodium salt. The neutral complexes of this anionic ligand with zinc(II), bismuth(III), and nickel(II) have beensynthesized and characterized by X-ray crystallography. In every complex, the ligand is coordinated to the metalin the S2 mode, generating eight-membered chelate rings. The bismuth and nickel complexes exhibit two M···H-Binteractions responsible for the dodecahedral and octahedral geometries, respectively. For the zinc complex, thetrigonal-bipyramidal coordination is achieved with an apical Zn···H-B interaction. The crystal structures for thethree complexes are described, and ab initio calculations on Bi(III), Ni(II), and Zn(II) compounds have been performedin order to assess the nature of the M···H-B interaction and its role for the definition of the molecular geometries.
C provides the new ligand dihydrobis(thioxotriazolinyl)borato, [BtEt,Me]-,as its sodium salt. The neutral complexes of this anionic ligand with zinc(II), bismuth(III), and nickel(II) have beensynthesized and characterized by X-ray crystallography. In every complex, the ligand is coordinated to the metalin the S2 mode, generating eight-membered chelate rings. The bismuth and nickel complexes exhibit two M···H-Binteractions responsible for the dodecahedral and octahedral geometries, respectively. For the zinc complex, thetrigonal-bipyramidal coordination is achieved with an apical Zn···H-B interaction. The crystal structures for thethree complexes are described, and ab initio calculations on Bi(III), Ni(II), and Zn(II) compounds have been performedin order to assess the nature of the M···H-B interaction and its role for the definition of the molecular geometries.