Salehzadeh Sadegh, Bayat Mehdi, Ward Michael D
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran.
J Phys Chem A. 2008 May 1;112(17):4090-4. doi: 10.1021/jp709603r. Epub 2008 Mar 19.
A theoretical study on the first protonation step of a series of metal complexes with the general formula {M(N[(CH2)nNH2][(CH2)mNH2][(CH2)pNH2])2+} (n = m = p = 2, tren; n = 3, m = p = 2, pee; n = m = 3, p = 2, ppe; n = m = p = 3, tpt; n = 2, m = 3, p = 4, epb; and n = m = 3, p = 4, ppb; and M = Zn2+) was reported using both the Hartree-Fock and DFT (B3LYP) levels of theory. For the first time, two kinds of our recently published definitions for gas-phase proton affinities of polybasic ligands, proton microaffinity and proton macroaffinity, were extended to their metal complexes. There is a good correlation between the calculated gas-phase proton macroaffinities and the corresponding formation constants in solution.
采用哈特里－福克方法和密度泛函理论（B3LYP），对通式为{M(N[(CH2)nNH2][(CH2)mNH2][(CH2)pNH2])2+}（n = m = p = 2，三联乙撑四胺；n = 3，m = p = 2，五乙撑六胺；n = m = 3，p = 2，三丙撑四胺；n = m = p = 3，三（2-氨基乙基）胺；n = 2，m = 3，p = 4，乙二胺丙撑二胺；n = m = 3，p = 4，三丙撑二胺；且M = Zn2+）的一系列金属配合物的第一步质子化反应进行了理论研究。首次将我们最近发表的两种关于多元配体气相质子亲合势的定义，即质子微亲合势和质子宏亲合势，扩展到其金属配合物。计算得到的气相质子宏亲合势与溶液中相应的形成常数之间存在良好的相关性。
