Electronic Structure Studies on Deprotonation of Dithiophosphinic Acids in Water Clusters

Adriana Dinescu; Michael T. Benson

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Electronic Structure Studies on Deprotonation of Dithiophosphinic Acids in Water Clusters

机译：水团中二硫代次膦酸去质子化的电子结构研究

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We report herein a computational study of proton transfer reactions between dithiophosphinic acids (HAs) and water clusters using B3LYP and MP2 methods. The ground-state and transition-state structures of HA-(H2O)_n(n = 1, 2, 3) cluster complexes have been calculated. The influence of water molecules on energy barrier heights of proton transfer reactions has been examined in the gas phase and solution for bis-[o-(trifluoromethyl)phenyl]- and bis(2,4,4-trimethyipentyl)dithiophosphinic acids (HA1 and HA2, respectively). Gas-phase calculations indicate that electron-withdrawing substituents and trifluoromethyl groups in the ortho position favor deprotonation of HA1 when three water molecules are included in the cluster. This suggests that at least three water molecules are necessary to solvate the abstracted proton in the presence of the anion. In the case of HA2, the electron-donating groups favor the reverse proton transfer reaction, namely, protonation of dithiophosphinate anion. Bulk solvent effects have been modeled for aqueous and organic media with the CPCM model. The calculated results show that polar solvents can lower the activation energy for less energetically stable transition states that have more localized charges.

机译：我们在此报告使用B3LYP和MP2方法进行的二硫代次膦酸（HAs）与水团簇之间质子转移反应的计算研究。 HA-（H2O）_n（n = 1，2，3）团簇配合物的基态和过渡态结构已经计算出来。在气相和双-[o-（三氟甲基）苯基]-和双（2,4,4-三甲基戊基）二硫代次膦酸（HA1和H2O2）溶液中研究了水分子对质子转移反应能垒高度的影响。 HA2）。气相计算表明，当簇中包含三个水分子时，邻位的吸电子取代基和三氟甲基有利于HA1的去质子化。这表明在阴离子的存在下，至少需要三个水分子来溶解提取的质子。在HA2的情况下，给电子基团有利于反向质子转移反应，即二硫代次膦酸根阴离子的质子化。已使用CPCM模型对水性和有机介质的整体溶剂效应进行了建模。计算结果表明，极性溶剂可以降低具有更多局部电荷的较低能量稳定过渡态的活化能。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2008年第47期|共11页
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Adriana Dinescu; Michael T. Benson;
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1. Electronic Structure Studies on Deprotonation of Dithiophosphinic Acids in Water Clusters [J] . Adriana Dinescu, Michael T. Benson The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2008,第47期

机译：水团中二硫代次膦酸去质子化的电子结构研究
2. Chemistry of styrene (water)(n) clusters, n=1-5: Spectroscopy and structure of the neutral clusters, deprotonation of styrene dimer cation, and implication to the inhibition of cationic polymerization [J] . Mahmoud H, Germanenko IN, Wright D, The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2005,第20期

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3. USING CLUSTER STUDIES TO APPROACH THE ELECTRONIC STRUCTURE OF BULK WATER - REASSESSING THE VACUUM LEVEL, CONDUCTION BAND EDGE, AND BAND GAP OF WATER [J] . Coe JV., Cohen MH., Hoffman GJ., The Journal of Chemical Physics . 1997,第16期

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4. Theoretical structures of triflic acid-water clusters and the molecular mechanism of proton dissociation [C] . Stephen J. Paddison, Lawrence R. Pratt, Thomas A. Zawodzinski Jr. International Symposium on Proton Conducting Membrane Fuel Cells . 1999

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Electronic Structure Studies on Deprotonation of Dithiophosphinic Acids in Water Clusters

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