Proton solvates, H+ • nH2O•mL, formed by diphosphine dioxides with chlorinated cobalt(III) dicarbollide acid
Proton solvates, H+ • nH2O•mL, formed by diphosphine dioxides with chlorinated cobalt(III) dicarbollide acid
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DOI：
10.1016/j.molstruc.2004.12.037
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发表时间：
2005-04-25
影响因子：
3.8
通讯作者：
Smirnov, IV
中科院分区：
文献类型：
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作者：
Stoyanov, ES;Smirnov, IV
研究了二氯乙烷溶液中水合质子H_5O_2+中心点(H_2O)(4)与含有甲基(Ph_4Me)、乙基(Ph_4Et)和聚氧乙烯(Ph(4)Reg)链连接的二苯基二膦氧化物(L)的相互作用。一种体积较大的反离子：氯化钴(III)双(二碳氢化物)，[Co(C(2)BqH(8)Cl(3))(2)](-)，使阳离子的扰动最小。在低浓度下，Ph_4Et和Ph(4)聚乙二醇与(P=)O-H~+-O(=P)片段形成1：1的无水络合物，具有很强的对称氢键。在这些条件下，Ph4Me形成了另一种化合物，H5O2+中心点L(H2O)(2)，这是因为较低的P=O碱度和最佳的络合循环几何构型。在较高浓度下，Ph_4Me和Ph_4Et与H_5O_2+形成等结构络合物H_5O_2+中心点L-2，而Ph(4)聚乙二醇只与二水质子形成1：1的络合物，H_3O+中心点H_2O超过游离Ph_4Me和Ph_4Et。在H_5O_2+的第一配位球上引入水分子，络合物的平均摩尔比L/H_5O_2+大于2。讨论了这些络合物的组成与L及其浓度的关系。(C)2005 Elsevier B.V.保留所有权利。
Interaction of hydrated proton, H5O2+ center dot (H2O)(4), in dichloroethane solutions with diphosphine dioxides (L) having methyl (Ph4Me), ethyl (Ph4Et) and polyoxyethylene chains (Ph(4)REG) linking two diphenyl phosphine oxide groups has been investigated. A bulky counter ion: chlorinated cobalt(III) bis(dicarbollide), [Co(C(2)BqH(8)Cl(3))(2)](-), minimizes perturbation of the cation. At low concentrations, Ph4Et and Ph(4)PEG form anhydrous 1:1 complexes with (P=)O-H+-O(=P) fragment having very strong symmetrical H-bonds. At these conditions Ph4Me form another compound, H5O2+ center dot L(H2O)(2), due to lower P=O basicity and optimal geometry of the chelate cycle. At higher concentrations, Ph4Me and Ph4Et form isostructural complexes H5O2+ center dot L-2, whereas Ph(4)PEG forms only a 1: 1 complex with proton dihydrate, H3O+ center dot H2O, In excess of free Ph4Me and Ph4Et a water molecule is introduced to the first coordination sphere of H5O2+ and the average molar ratio L/H5O2+ of the complexes exceeds 2. The composition of these complexes as a function of L and its concentration is discussed. (c) 2005 Elsevier B.V. All rights reserved.