Abstract
An IR spectroscopic study has established that in water-dichloroethane equilibrium solutions, carbamoylphosphine oxide forms only one complex with HNO3, R'R2P=O...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 depends on the molar ratio CCMPO \(C_{{\text{HCIO}}_{\text{4}} }\) and the solution preparation temperature. A CMPO:HClO4 = 2:1 complex is formed when CCMPO/\(C_{{\text{HCIO}}_{\text{4}} }\) > 2; for CCMPO/C\(C_{{\text{HCIO}}_{\text{4}} }\) <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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
V. N. Romanovskii, V. M. Esimantovskii, I. V. Smirnov, et al., Solv. Extr. Ion Exch., 19 No.1, 1-21 (2001).
J. D. Law, R. S. Herbst, T. A. Todd, et al., ibid., 19 No.1, 23-36 (2001).
R. J. H. Clarc and R. E. Hester (eds.), Advances in Infrared and Raman Spectroscopy, Heiden, London (1976), p. 343.
E. S. Stoyanov, Zh. Strukt. Khim., 33 No.6, 57-62 (1992).
E. S. Stoyanov, J. Chem. Soc.,Faraday Trans., 93 No.23, 4165-4175 (1997).
E. S. Stoyanov and V. N. Kolomiichuk, Mendeleev Commun., 180-182 (1997).
E. S. Stoyanov, J. Chem. Soc., Faraday Trans., 94, 2803-2812 (1998).
E. S. Stoyanov, V. A. Mikhailov, and A. M. Chekmarev, Zh. Neorg. Khim., 35 No.6, 1442-1450 (1990).
S. Detoni and D. Hadsi, Spectrochim. Acta, 20, 949-955 (1964).
M. F. Claydon and N. J. Sheppard, J. Chem. Soc. D, No.23, 1431-1433 (1969).
S. E. Odinokov and A. V. Iogansen, Spectrochim. Acta, 28A No.12, 2343-2350 (1972).
S. P. Khranenko, “Investigation of the extraction mechanism of HTlCl4 from chloride-sulfate solutions with neutral organophosphorus solutions, ” Chemical Sciences Candidate 's Dissertation, Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk (1973).
E. S. Stoyanov, Mendeleev Commun., 190-192 (1999).
E. S. Stoyanov, Phys. Chem. Chem. Phys., 2, 1137-1145 (2000).
E. S. Stoyanov, V. A. Mikhailov, A. M. Chekmarev, and S. V. Chizhevskaya, Zh. Neorg. Khim., 35 No.6, 1451-1459 (1990).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Stoyanov, E.S., Vorob'yova, T.P. & Smirnov, I.V. Complexation of Carbamoylphosphine Oxide with Nitric and Perchloric Acids in Water-Dichloroethane Equilibrium Solutions. Journal of Structural Chemistry 44, 365–375 (2003). https://doi.org/10.1023/B:JORY.0000009662.06643.3b
Issue Date:
DOI: https://doi.org/10.1023/B:JORY.0000009662.06643.3b