Programa de Pós-Graduação em Química, Instituto de Química, Universidade Federal Fluminense, Outeiro de São João Batista, s/n, 24020-141 Niterói, RJ, Brazil.
J Mol Model. 2011 Aug;17(8):2061-7. doi: 10.1007/s00894-010-0909-z. Epub 2010 Dec 14.
DFT (B3LYP/6-31+G(d)) calculations of Mg(2+) affinities for a set of phosphoryl ligands were performed. Two types of ligands were studied: a set of trivalent [O = P(R)] and a set of pentavalent phosphoryl ligands [O = P(R)(3)] (R = H, F, Cl, Br, OH, OCH(3), CH(3), CN, NH(2) and NO(2)), with R either bound directly to the phosphorus atom or to the para position of a phenyl ring. The affinity of the Mg(2+) cation for the ligands was quantified by means of the enthalpy for the substitution of one water molecule in the Mg(H(2)O)(6) complex for a ligand. The enthalpy of substitution was correlated with electronic and geometric parameters. Electron-donor groups increase the interaction between the cation and the ligand, while electron-acceptor groups decrease the interaction enthalpy.
采用 DFT（B3LYP/6-31+G(d)）方法计算了一组磷酸配体与 Mg(2+)亲和力。研究了两种类型的配体：一组三价 [O = P(R)] 和一组五价磷酸配体 [O = P(R)(3)]（R = H、F、Cl、Br、OH、OCH(3)、CH(3)、CN、NH(2) 和 NO(2)），其中 R 直接与磷原子或苯环的对位相连。通过取代 Mg(H(2)O)(6)配合物中的一个水分子与配体的焓来定量化 Mg(2+)阳离子与配体的亲和力。取代焓与电子和几何参数相关联。供电子基团增加了阳离子与配体之间的相互作用，而吸电子基团降低了相互作用焓。
