Proton Solvates, H+·nH2O·mL, Formed by Diphosphine Dioxides with Chlorinated Cobalt(III) Dicarbollide Acid Full article
Journal |
Journal of Molecular Structure
ISSN: 0022-2860 |
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Output data | Year: 2005, Volume: 740, Number: 1-3, Pages: 9-16 Pages count : 8 DOI: 10.1016/j.molstruc.2004.12.037 | ||||
Tags | Diphosphine dioxides, IR spectroscopy, Proton hydrates and solvates, Strong H-bonds | ||||
Authors |
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Affiliations |
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Funding (2)
1 | Civilian Research and Development Foundation | RC2-2342-ST-02 |
2 | United States Department of Energy | 81995 |
Abstract:
Interaction of hydrated proton, H5O2+·(H2O)4, in dichloroethane solutions with diphosphine dioxides (L) having methyl (Ph4Me), ethyl (Ph4Et) and polyoxyethylene chains (Ph4PEG) linking two diphenyl phosphine oxide groups has been investigated. A bulky counter ion: chlorinated cobalt(III) bis(dicarbollide), [Co(C2B9H8Cl3)2]−, minimizes perturbation of the cation. At low concentrations, Ph4Et and Ph4PEG form anhydrous 1:1 complexes with (P6-point double bond; length half of m-dash)O–H+–O(6-point double bond; length half of m-dashP) fragment having very strong symmetrical H-bonds. At these conditions Ph4Me form another compound, H5O2+·L(H2O)2, due to lower P6-point double bond; length half of m-dashO basicity and optimal geometry of the chelate cycle. At higher concentrations, Ph4Me and Ph4Et form isostructural complexes H5O2+·L2, whereas Ph4PEG forms only a 1:1 complex with proton dihydrate, H3O+·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.
Cite:
Stoyanov E.S.
, Smirnov I.V.
Proton Solvates, H+·nH2O·mL, Formed by Diphosphine Dioxides with Chlorinated Cobalt(III) Dicarbollide Acid
Journal of Molecular Structure. 2005. V.740. N1-3. P.9-16. DOI: 10.1016/j.molstruc.2004.12.037 WOS Scopus РИНЦ
Proton Solvates, H+·nH2O·mL, Formed by Diphosphine Dioxides with Chlorinated Cobalt(III) Dicarbollide Acid
Journal of Molecular Structure. 2005. V.740. N1-3. P.9-16. DOI: 10.1016/j.molstruc.2004.12.037 WOS Scopus РИНЦ
Dates:
Submitted: | Oct 15, 2004 |
Accepted: | Dec 21, 2004 |
Published online: | Feb 8, 2005 |
Published print: | Apr 25, 2005 |
Identifiers:
Web of science | WOS:000229207700002 |
Scopus | 2-s2.0-16344382751 |
Elibrary | 13485624 |
Chemical Abstracts | 2005:314572 |
Chemical Abstracts (print) | 143:48623 |
OpenAlex | W1985703716 |