Effect of substituents on ionization potentials of phosphorus compounds. Conjugation in radical cations |
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Authors: | Egorochkin A N Voronkov M G Skobeleva S E Zderenova O V |
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Institution: | (1) G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603600 Nizhnii Novgorod, Russian Federation;(2) Irkutsk Institute of Chemistry, Siberian Branch of the, Russian Academy of Sciences, 1 ul. Favorskogo, 664033 Irkutsk, Russian Federation |
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Abstract: | The first vertical ionization potentials (I) of phosphorus compounds P(Xi)3, OP(Xi)3, SP(Xi)3, (4-XC6H4)3P, and PCX are related to the inductive, resonance, and polarizability parameters of inorganic, organic, and organometallic substituents X by dependences of the type I = I
H + aI + bR
+ + c, where I
H is the I value for X = H. The I values are also affected by hyperconjugation. The ratio of the contributions of the resonance (bR
+) and polarizability (c) effects to the I value is determined by the degree of delocalization of the unpaired electron and the positive charge in the radical cations formed upon ionization of neutral molecules. The R
+ resonance parameters of organosilicon, organogermanium, and organotin substituents bound to the P
·+ radical cation center were calculated for the first time. |
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Keywords: | organophosphorus compounds phosphorus compounds containing P--Si P--Ge and P--Sn bonds ionization potential radical cation conjugation polarizability of substituents |
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