TY - JOUR

T1 - Complexation of carbamoylphosphine oxide with nitric and perchloric acids in water-dichloroethane equilibrium solutions

AU - Stoyanov, E. S.

AU - Vorob'yova, T. P.

AU - Smirnov, I. V.

PY - 2003/5/1

Y1 - 2003/5/1

N2 - An IR spectroscopic study has established that in water-dichloroethane equilibrium solutions carbamoylphosphine oxide forms only one complex, R′R2P=O⋯HNO3, with HNO3, whereas with HClO4 it forms a number of solvation-separated ion pairs (IP). The structure and composition of the cation moiety of these IP depend on the molar ratio CCMPO/CHClO4 and the solution preparation temperature. A CMPO:HClO4 = 2:1 complex is formed when C CMPO/CHClO4 > 2; for CCMPO/CHClO4 < 2, 1:1 and 1:2 complexes and a complex with HClO4 attached to the tertiary nitrogen of CMPO are formed. A detailed discussion is given for all complexes. It is shown for the first time that H+ can interact with three oxygen atoms of two P=O groups and one C=O group (or a water molecule) at once. In the absence of CMPO, dichloroethane extracts HNO3 in the form of micelle-like associates, whose nucleus has a solubilized HNO3 molecule in the form of a solvation-separated IP.

AB - An IR spectroscopic study has established that in water-dichloroethane equilibrium solutions carbamoylphosphine oxide forms only one complex, R′R2P=O⋯HNO3, with HNO3, whereas with HClO4 it forms a number of solvation-separated ion pairs (IP). The structure and composition of the cation moiety of these IP depend on the molar ratio CCMPO/CHClO4 and the solution preparation temperature. A CMPO:HClO4 = 2:1 complex is formed when C CMPO/CHClO4 > 2; for CCMPO/CHClO4 < 2, 1:1 and 1:2 complexes and a complex with HClO4 attached to the tertiary nitrogen of CMPO are formed. A detailed discussion is given for all complexes. It is shown for the first time that H+ can interact with three oxygen atoms of two P=O groups and one C=O group (or a water molecule) at once. In the absence of CMPO, dichloroethane extracts HNO3 in the form of micelle-like associates, whose nucleus has a solubilized HNO3 molecule in the form of a solvation-separated IP.

KW - Acid extraction

KW - Hydrated proton

KW - IR spectroscopy

KW - Protonation of carbamoylphosphine oxide

UR - http://www.scopus.com/inward/record.url?scp=0347603835&partnerID=8YFLogxK

U2 - 10.1023/B:JORY.0000009662.06643.3b

DO - 10.1023/B:JORY.0000009662.06643.3b

M3 - Article

AN - SCOPUS:0347603835

VL - 44

SP - 365

EP - 375

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 3

ER -