Te
Te interactions in inorganic rings with sulfur donors
Te interactions in inorganic rings with sulfur donors
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- 作者：Bandeira ; Nuno A.G. ; Veiros ; Luí ; s F. ; Calhorda ; Maria J. ; Novosad ; Josef
- 关键词：Inorganic rings ; Te compounds ; Se compounds ; X-ray structures ; DFT calculations ; MP2 calculations
- 刊名：Inorganica Chimica Acta
- 出版年：2003
- 出版时间：December 3, 2003
- 年：2003
- 卷：356
- 期：Complete
- 页码：319-327
- 全文大小：635 K
文摘
Te(II) forms binuclear complexes with bridging [{S
P(Ph)2}2N]− ligands and axial aryl groups with very long Te
Te distances, while Te(I) analogues with [S2P(R)2]− have no axial ligands and exhibit a TeTe bond. No such selenium complexes have been found, although a square-planar mononuclear derivative of [{SP(Ph)2}2N]− is available for both Te and Se. In an attempt to study the nature of the TeTe interaction, a variety of theoretical approaches and basis sets was used in order to find the best way to reproduce the TeTe distance in the Te(II) derivatives. DFT calculations with the ADF program provided the best answer, since MP2 calculations are more computationally demanding. While the formal oxidation state of Te is a requirement for a TeTe bond, the type of ligand strongly determines the geometry of the binuclear species. The smaller [S2P(R)2]− leads to more asymmetric species, with Te forming a normal TeS bond and a very weak one; with [{SP(Ph)2}2N]−, both TeS bonds have comparable lengths. Selenium analogues were found to behave similarly.
P(Ph)2}2N]− ligands and axial aryl groups with very long TeTe distances, while Te(I) analogues with [S2P(R)2]− have no axial ligands and exhibit a TeTe bond. No such selenium complexes have been found, although a square-planar mononuclear derivative of [{SP(Ph)2}2N]− is available for both Te and Se. In an attempt to study the nature of the TeTe interaction, a variety of theoretical approaches and basis sets was used in order to find the best way to reproduce the TeTe distance in the Te(II) derivatives. DFT calculations with the ADF program provided the best answer, since MP2 calculations are more computationally demanding. While the formal oxidation state of Te is a requirement for a TeTe bond, the type of ligand strongly determines the geometry of the binuclear species. The smaller [S2P(R)2]− leads to more asymmetric species, with Te forming a normal TeS bond and a very weak one; with [{SP(Ph)2}2N]−, both TeS bonds have comparable lengths. Selenium analogues were found to behave similarly.