Abstract
The first vertical ionization potentialsI(ns) of 69 monosulfides XSY (X, Y=H, Hal, organic, or heteroorganic substituent) are related to the inductive σI resonance (σ +R ) and polarizability (σα) constants of the substituents by dependences of theI(nS)=a+bΣσI+bΣσR+bΣσα type. TheI(ns) values are also affected by hyperconjugation which increases on going from XSH to XSY (Y≠H) compounds. The first calculations of the σ +R parameters characterizing the conjugation of Si-, Ge-, Sn-, and Pb-containing substituents with the S.+ radical cation center are reported. The reasons for weakening of resonance donor properties of heteroorganic substituents of the +M-type in the systems studied as compared to those of the same substituents in the corresponding aromatic radical cations are considered.
Similar content being viewed by others
References
A. N. Egorochkin,Usp. Khim., 1992,61, 1092 [Russ. Chem. Rev., 1992,61, 600 (Engl. Transl.)].
A. N. Egorochkin and G. A. Razuvaev,Usp. Khim., 1987,56, 1480 [Russ. Chem. Rev., 1987,56, 846 (Engl. Transl.)].
A. N. Egorochkin,Usp. Khim., 1984,53, 772 [Russ. Chem. Rev., 1984,53, 445 (Engl. Transl.)].
A. N. Egorochkin, S. E. Skobeleva, E. T. Bogoradovsky, and T. P. Zubova,Izv. Akad. Nauk, Ser. Khim., 1994, 1041 [Russ. Chem. Bull., 1994,43, 976 (Engl. Transl.)].
A. N. Egorochkin, S. E. Skobeleva, and T. G. Mushtina,Izv. Akad. Nauk, Ser. Khim., 1998, 1481 [Russ. Chem. Bull., 1998,47, 1436 (Engl. Transl.)].
A. N. Egorochkin, S. E. Skobeleva, and T. G. Mushtina,Izv. Akad. Nauk, Ser. Khim., 1998, 2434 [Russ. Chem. Bull., 1998,47, 2352 (Engl. Transl.)].
V. I. Nefedov and V. I. Vovna,Elektronnaya struktura organicheskikh i elementoorganicheskikh soedinenii [The Electronic Structure of Organic and Organoelement Compounds], Nauka, Moscow, 1989 (in Russian).
I. A. Koppel', U. Kh. Mel'der, and R. I. Pikver,Reakts. Sposobn. Organ. Soedinenii, 1981,18, 366 [Organic Reactivity, 1981,18 (Engl. Transl.)].
V. I. Nefedov and V. I. Vovna,Elektronnaya struktura khimicheskikh soedinenii [The Electronic Structure of Chemical Compounds], Nauka, Moscow, 1987 (in Russian).
C. Hansch, A. Leo, and R. W. Taft,Chem. Rev., 1991,91, 165.
S. N. Mazalov and V. D. Yumatov,Elektronnoe stroenie ekstragentov [The Electronic Structure of Extractive Agents], Nauka, Novosibirsk, 1984 (in Russian).
D. P. Chong, F. G. Herring, and D. McWilliams,J. Chem. Phys., 1974,61, 78.
S. Marriott and R. D. Topsom,J. Mol. Struct., 1984,106, 277.
P. D. Pacey and Q.-T. N. Tan,J. Phys. Chem., 1995,99, 17729.
R. W. Taft and R. D. Topsom,Prog. Phys. Org. Chem., 1987,16, 1.
W. F. Reynolds, P. Dais, D. W. MacIntyre, R. D. Topsom, S. Marriott, E. von Nagy-FeIsobuki, and R. W. Taft,J. Am. Chem. Soc., 1983,105, 378.
H. Kwart and K. King,d-Orbitals in the Chemistry of Silicon, Phosphorus, and Sulphur, Springer, Berlin, 1977.
H. Bock and B. Solouki, inThe Chemistry of Organic Silicon Compounds, eds. S. Patai and Z. Rappoport, Wiley, Chichester, 1989, Pt. 1, 555.
H. Bock and B. Solouki,Chem. Rev., 1995,95, 1161.
G. Distefano, A. Ricci, F. P. Colonna, D. Pietropaolo, and S. Pignataro,J. Organomet. Chem., 1974,78, 93.
A. I. Ermakov, N. A Makrushin, M. S. Sorokin, V. I. Kleimenov, E. A. Kirichenko, and M. G. Voronkov,Izv. Akad. Nauk SSSR, Ser. Khim., 1986, 1105 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1986,35, 1001 (Engl. Transl.)].
R. W. Taft, I. A. Koppel, R. D. Topsom, and F. Anvia,J. Am. Chem. Soc., 1990,112, 2047.
A. N. Egorochkin, S. E. Skobeleva, V. L. Tsvetkova, E. T. Bogoradovsky, and V. S. Zavgorodny,Metalloorg. Khim., 1992,5, 1342 [Organomet. Chem. USSR, 1992,5 (Engl. Transl.)].
A. N. Egorochkin, S. E. Skobeleva, E. T. Bogoradovsky, and T. P. Zubova,Izv. Akad. Nauk, Ser. Khim., 1994, 2252 [Russ. Chem. Bull., 1994,43, 2131 (Engl. Transl.)].
A. N. Egorochkin, S. E. Skobeleva, and T. G. Mushtina,Izv. Akad. Nauk, Ser. Khim., 1997, 1626 [Russ. Chem. Bull., 1997,46, 1549 (Engl. Transl.)].
Author information
Authors and Affiliations
Additional information
Translated fromIzvestiya Akademii Nauk. Seriya Khmicheskaya, No. 1, pp. 25–31, January, 2000.
Rights and permissions
About this article
Cite this article
Egorochkin, A.N., Voronkov, M.G., Skobeleva, S.E. et al. Ionization potentials of non-metal monosulfides. Conjugation in radical cations containing Group IV elements. Russ Chem Bull 49, 26–32 (2000). https://doi.org/10.1007/BF02499060
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02499060