对非刚性六配位化合物[Mo(R)F5]、[W(R)F5]及相关化合物的理论研究。

A theoretical investigation of the nonrigid six-coordinate compounds [Mo(R)F5], [W(R)F5], and related compounds.

作者信息

Quiñones Gustavo Santiso, Seppelt Konrad

机构信息

Freie Universität Berlin, Institut für Chemie, Anorganische und Analytische Chemie, Fabeckstrasse 34-36, 14195 Berlin, Germany.

出版信息

Chemistry. 2006 Feb 8;12(6):1790-6. doi: 10.1002/chem.200500248.

DOI:10.1002/chem.200500248

PMID:16331709

Abstract

Density functional calculations for [M(CH3)F5], [M(CF3)F5], [M(CH3S)F5], and [M(CF3S)F5] (M=Mo, W) show that they are expected to be nonrigid molecules, with energy barriers for the octahedral-trigonal-prismatic interchange as low as 7.2 kJ mol(-1). The ground state for the CH3- and CF3- compounds is trigonal prismatic, for the CH3S- and CF3S- compounds, (distorted) octahedral. All calculated compounds [M(C6F5)nF(6-n)] (M=Mo, W) have a trigonal-prismatic ground state, whereas the situation for [M(C6H5)nF(6-n)] (M=Mo, W) is more complex.

摘要

对[M(CH₃)F₅]、[M(CF₃)F₅]、[M(CH₃S)F₅]和[M(CF₃S)F₅]（M = Mo、W）进行的密度泛函计算表明，它们预计为非刚性分子，八面体 - 三角棱柱体互换的能垒低至7.2 kJ mol⁻¹。CH₃ - 和CF₃ - 化合物的基态为三角棱柱体，CH₃S - 和CF₃S - 化合物的基态为（扭曲的）八面体。所有计算出的化合物[M(C₆F₅)ₙF(₆₋ₙ)]（M = Mo、W）都具有三角棱柱体基态，而[M(C₆H₅)ₙF(₆₋ₙ)]（M = Mo、W）的情况则更为复杂。