The Origin of Endocyclic Bond Length Variations in Disubstituted Cyclotriphosphazenes

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• 作者：Michael Calichman ; Agnes Derecskei-Kovacs ; Christopher W. Allen
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：March 19, 2007
• 年：2007
• 卷：46
• 期：6
• 页码：2011 - 2016
• 全文大小：85K
• 年卷期：v.46,no.6(March 19, 2007)
• ISSN：1520-510X

文摘

Intraannular ring alternation in heterogeneously substituted cyclotriphosphazenes is investigated using both abinitio and density functional methods. Comparisons of the calculated geometries for N₃P₃X₆ (X = H, F, Cl, Me, Ph)and N₃P₃X₄Y₂ (X = F, Cl; Y = Me, Ph, X, Cl) with experimental X-ray data establish the utility of the 6-31G* basisfor use with both Hartree-Fock and the B3LYP and B3PW91 functionals. Analysis of orbitals and charges showsthat the bonding is best described using a polarized bond model rather than the previous explanation of asymmetricnitrogen-lone-pair donation into the phosphorus-nitrogen bond.