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Title: Hydrogen bonding in aggregates of dialkyl-substituted diphosphonic acids and monofunctional analogues

Abstract

Hydrogen bonding of dialkyl-substituted diphosphonic acids in nonpolar (toluene and CCl{sub 4}) and alcohol (1-decanol) solutions is examined. The compounds are monomeric in 1-decanol and dimeric or higher in nonpolar organic diluents. Infrared spectroscopy and molecular mechanics calculations suggest that the dimers of P,P{prime}-di(2-ethylhexyl) methanediphosphonic acid (H{sub 2}DEH[MDP]) and its straight-chain isomer, P,P{prime}-dioctyl methanediphosphonic acid (H{sub 2}DO[MDP]), adopt rigid highly hydrogen-bonded structures such as C or D. The homologous P,P{prime}-di(2-ethylhexyl) ethane- and butanediphosphonic acids, H{sub 2}DEH[EDP] and H{sub 2}DEH[BuDP], respectively adopt structures that are also intermolecularly hydrogen-bonded but more flexible. The effect on the P+O stretching vibration of increasing 1-decanol concentration in the solvent differs for these compounds. In the case of H{sub 2}DEH[MDP] and H{sub 2}DO[MDP], the frequency remains constant until all CCl{sub 4} has been replaced by the alcohol, then the P=O stretching frequency shifts to a lower energy. In the case of H{sub 2}DEH[edp] and H{sub 2}DEH[BuDP], a gradual shift to higher energy occurs as the alcohol concentration increases. The magnitude of the difference in the P=O stretching frequencies between CCL{sub 4} and 1-decanol solution is greatest for organophosphonic acids, less for organodiphosphonic acids, and least for organophosphoric acids.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab., IL (US)
Sponsoring Org.:
USDOE
OSTI Identifier:
20000555
DOE Contract Number:  
W-31109-ENG-38
Resource Type:
Journal Article
Journal Name:
Solvent Extraction and Ion Exchange
Additional Journal Information:
Journal Volume: 17; Journal Issue: 5; Other Information: PBD: Sep 1999; Journal ID: ISSN 0736-6299
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; PHOSPHONIC ACIDS; AGGLOMERATION; CHEMICAL BONDS; HYDROGEN; CARBON TETRACHLORIDE; TOLUENE; DECANOLS; CHELATING AGENTS; SOLVENT EXTRACTION; ACTINIDES; RARE EARTHS

Citation Formats

Barrans, R.E. Jr., McAlister, D.R., Herlinger, A.W., Chiarizia, R., and Ferraro, J.R. Hydrogen bonding in aggregates of dialkyl-substituted diphosphonic acids and monofunctional analogues. United States: N. p., 1999. Web. doi:10.1080/07366299908934643.
Barrans, R.E. Jr., McAlister, D.R., Herlinger, A.W., Chiarizia, R., & Ferraro, J.R. Hydrogen bonding in aggregates of dialkyl-substituted diphosphonic acids and monofunctional analogues. United States. doi:10.1080/07366299908934643.
Barrans, R.E. Jr., McAlister, D.R., Herlinger, A.W., Chiarizia, R., and Ferraro, J.R. Wed . "Hydrogen bonding in aggregates of dialkyl-substituted diphosphonic acids and monofunctional analogues". United States. doi:10.1080/07366299908934643.
@article{osti_20000555,
title = {Hydrogen bonding in aggregates of dialkyl-substituted diphosphonic acids and monofunctional analogues},
author = {Barrans, R.E. Jr. and McAlister, D.R. and Herlinger, A.W. and Chiarizia, R. and Ferraro, J.R.},
abstractNote = {Hydrogen bonding of dialkyl-substituted diphosphonic acids in nonpolar (toluene and CCl{sub 4}) and alcohol (1-decanol) solutions is examined. The compounds are monomeric in 1-decanol and dimeric or higher in nonpolar organic diluents. Infrared spectroscopy and molecular mechanics calculations suggest that the dimers of P,P{prime}-di(2-ethylhexyl) methanediphosphonic acid (H{sub 2}DEH[MDP]) and its straight-chain isomer, P,P{prime}-dioctyl methanediphosphonic acid (H{sub 2}DO[MDP]), adopt rigid highly hydrogen-bonded structures such as C or D. The homologous P,P{prime}-di(2-ethylhexyl) ethane- and butanediphosphonic acids, H{sub 2}DEH[EDP] and H{sub 2}DEH[BuDP], respectively adopt structures that are also intermolecularly hydrogen-bonded but more flexible. The effect on the P+O stretching vibration of increasing 1-decanol concentration in the solvent differs for these compounds. In the case of H{sub 2}DEH[MDP] and H{sub 2}DO[MDP], the frequency remains constant until all CCl{sub 4} has been replaced by the alcohol, then the P=O stretching frequency shifts to a lower energy. In the case of H{sub 2}DEH[edp] and H{sub 2}DEH[BuDP], a gradual shift to higher energy occurs as the alcohol concentration increases. The magnitude of the difference in the P=O stretching frequencies between CCL{sub 4} and 1-decanol solution is greatest for organophosphonic acids, less for organodiphosphonic acids, and least for organophosphoric acids.},
doi = {10.1080/07366299908934643},
journal = {Solvent Extraction and Ion Exchange},
issn = {0736-6299},
number = 5,
volume = 17,
place = {United States},
year = {1999},
month = {9}
}