M. V. Tsikalova

ESR study of adducts of diisopropylphosphoryl radicals with C60C[P(O)(OEt)2]22 isomers

The radical adducts of the P·(O)(OPri)2 (R·) radicals with C60C[P(O)(OEt)2]22 fullerene derivatives were studed by ESR spectroscopy. The number of stable regioisomers of phosphorylfullerenyl radicals formed by addition of the phosphoryl radicals to the C60C[P(O)(OEt)2]22 isomers depends on the mutual position of the organophosphorus groups and decreases in the series trans-2 > trans-3 ≈ trans-4 > e. The rate constants for addition of the R· radicals to the trans-3 regioisomer (k = 1.7·108 L mol–1 s–1) were determined.

Spin-adducts of radicals ·P(O)(OPri)2 and ·CMe3 with pyrrolidino[60]fullerenes studied by ESR spectroscopy

The addition of the ·But (R1) and ·P(O)(OPri)2 (R2) radicals to pyrrolidino[60]fullerenes C60CH2NMeCHX (X = C6H4N(CH2CH2Cl)2, 2,6-(But)2C6H2OH, PhC6H4, and indol-3-yl) was studied by ESR spectroscopy. The rate constants of R1 radical addition to these compounds and dimerization of spin-adducts of the R1 radicals with pyrrolidino[60]fullerenes were determined. Pyrrolidino[60]fullerenes manifest considerably higher reactivity toward the R1 radicals than fullerene C60 and methanofullerenes C60CX1X2 (X1 = X2 = CO2Et; X1 = CO2Me, X2 = OP(OMe)2, X1 = X2 = OP(OEt)2).

Influence of the Metallofragment on the Regioselectivity in the Addition of the Radicals •CCl3 and •But to (η2‐C60)Ir H(CO) (PPh3)2, (η2‐C60)Ir H(CO)[(+)DIOP], (η2‐C60)Os(CO)(PPh3)2(CNBut) and on the Stability of the Spin‐adducts

In this paper we have present the results of study for electronic influence of the metal fragment on the regioselectivity of addition of •CCl3 (R1 ) and •Bu t (R2 ) radicals to the complexes (η2‐C60)IrH(CO)(PPh3)2 (I), (η2‐C60)IrH(CO)[(+)DIOP] (II), (η2‐C60)Os(CO)(PPh3)2(CNBut) (III) and on the stability of spin‐adducts (SA). It was found that the addition of R1 and R2 to I–III unlike methano‐ or pyrrolidinofullerenes the ESR spectra exhibit signals from some regio‐isomers which substantial different by the g‐factor. The assignment of the individual signals to definite regio‐isomers was made. The rate constants of the addition of radicals R1 and R2 to carbon atoms of individual bonds in I–III were determined using the method of competing reactions.