Abstract
Coordination of dimethylsulfoxide molecules to the sodium and potassium cations was investigated by HF/6-31G(d)//HF/6-31G(d) and DFT(B3LYP/6-31G(d)) quantum-chemical methods. The coordination numbers of Na+ and K+ are found to be five and six, respectively. Thermal effects of complexation were calculated for each stage of the process; these were found to be 197.8, 160.1, 106.9, 88.0, 53.9 [HF/6-31G(d)] and 195.0, 158.5, 108.9, 95.7, 60.0 kJ/mole [B3LYP/6-31G(d)] for Na+ (one to five DMSO molecules, respectively); 146.6, 118.7, 90.2, 68.9, 70.0, 49.0 [HF/6-31G(d)] and 144.0, 117.4, 91.7, 78.9, 78.6, 56.4 kJ/mole [B3LYP/6-31G(d)] for K+ (one to six DMSO molecules, respectively). Structural parameters and charge distributions are given for the complexes. It is shown that solvation of sodium and potassium cations by DMSO molecules is preferable to solvation by water molecules.
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REFERENCES
A.I. Mikhaleva and N.K. Gusarova, Acetylenes:Reactions and Derivatives,Bibliography of the Scientific Works of B.A.Trofimov [in Russian ], Siberian Branch,Russian Academy of Sciences, Novosibirsk (1999),p.18.
B.A. Trofimov, S.V. Amosova, A.I. Mikhaleva,et al., Fundamental Research.Chemical Sciences [in Russian ], Nauka, Novosibirsk (1977),pp.174–178.
B.A. Trofimov, Heteroatomic Derivatives of Acetylene.New Polyfunctional Monomers,Reagents,and Intermediates [in Russian ], Nauka, Moscow (1981).
B.A. Trofimov, Usp.Khim., 50, 248–272 (1981).
B.A. Trofimov and A.I. Mikhaleva, N-Vinylpyrroles [in Russian ], Nauka, Novosibirsk (1984),pp.10–14.
B.A. Trofimov, Zh.Org.Khim., 22,No.9, 1991–dy2006 (1986).
B.A. Trofimov, T.N. Rakhmatulina, N.K. Gusarova, and S.F. Malysheva, Usp.Khim., 60, No.12, 2619–2632 (1991).
B.A. Trofimov, Sulfur Rep., 11, 207–231 (1992).
G. Suzukamo, M. Fukao, T. Hibi,et al.,in: Acid-Base Catalysis,Proc.Symp.Acid-Base Catalysis, K. Tanabe et al. (eds.), Kodasha (1989),p.405.
N.M. Vitkovskaya,”Quantum-chemical models of the elementary acts of acetylene reactions:Metal coordination and nucleophilic addition,” Chemical Doctoral Dissertation, Irkutsk (1986),p.42.
N.M. Vitkovskaya, O.Yu. Dolgunicheva, F.S. Dubnikova, and B.A. Trofimov, Izv.Akad.Nauk SSSR,Ser.Khim., 1335–1339 (1988).
N.M. Vitkovskaya, O.Yu. Dolgunicheva, F.S. Dubnikova, and B.A. Trofimov, ibid.,1339-1342.
B.A. Trofimov, Curr.Org.Chem., 6, 1121–1162 (2002).
Yu.L. Frolov, I.V. Guchik, V.A. Shagun,et al., Zh.Strukt.Khim., 44, No.6, 1005–1010 (2003).
J. Gordon, Organic Chemistry of Electrolyte Solutions [Russian translation ], Mir, Moscow (1979),p.300.
G.A. Krestov, V.N. Afanasiev, A.V. Agafonov,et al., Complexation in Nonaqueous Solutions [in Russian ], Nauka, Moscow (1989).
H. Ohtaki and T. Radnai, Chem.Rev., 93, 1157–1204 (1993).
V.J. Hehre, L. Radom, P.V.R. Schleyer, and J.A. Pople, Ab Initio Molecular Orbital Theory [in Russian ], Wiley, New York (1986),p.300.
H. Williams, G.M. Maggiora, and R.L. Schowen, J.Am.Chem.Soc., 102, 783 (1980).
M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al., Gaussian 98,Revision A.6, Gaussian Inc., Pittsburg PA (1998).
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Guchik, I.V., Frolov, Y.L., Shagun, V.A. et al. Quantum-Chemical Analysis of Coordination of Dimethylsulfoxide Molecules to Sodium and Potassium Cations. Journal of Structural Chemistry 45, 41–46 (2004). https://doi.org/10.1023/B:JORY.0000041499.95749.ed
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DOI: https://doi.org/10.1023/B:JORY.0000041499.95749.ed