The quantum chemical investigations of some representative bis-adducts of C60, C60O2, C60（NH）2, C60（CH2NHCH2）2 and C60（SO4）2 have been carried out at the AM1 and PM3 semi-empirical molecular orbital levels. The ...The quantum chemical investigations of some representative bis-adducts of C60, C60O2, C60（NH）2, C60（CH2NHCH2）2 and C60（SO4）2 have been carried out at the AM1 and PM3 semi-empirical molecular orbital levels. The relative energies of various isomers of these C60 bis-adducts have been calculated. For C60O2 and C60（NH）2 with the sterically non-demanding addends, cis-1 isomer resulted from 1,2-additions to adjacent 6/6 ring fusion is the lowest energy structure; for C60（CH2NHCH2）2 and C60（SO4）2 with sterically demanding addends, the most energetically preferred structure is e isomer. This is consistent with and enhances the general rule for regio-selectivity of fullerene C60 established by Hirsch, though Hirschs rule is summarized on the basis of methanofullerenes. The thermodynamic analysis is not significant to explain the experimentally observed regiochemistry for C60 bis-adducts, and the kinetic reasons or mechanisms may dominant in determining the regioselectivity of fullerene bis-adducts. Further addition patterns for multiple addition were also discussed.展开更多
At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and 4 dimethylamine pyridine which affords the last products as binuclear copper?complex (1), [Cu(C6H5COO)2(C7H...At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and 4 dimethylamine pyridine which affords the last products as binuclear copper?complex (1), [Cu(C6H5COO)2(C7H10N2)]2. This complex is further characterized by spectroscopic methods. The structure of complex (1) has been determined by a single crystal X ray analysis. Crystallographic data are as follows: monoclinic, space group P21/n, a=10.446(2)?, b=11.140(5)?, c=17.179(3)?, β=95.92(3)°, V=1988.4(7)?3, Z=4, F(000)=884, μ=11.27cm-1, D(calcd.)=1.429g·cm-3, R=0.0399, Rw=0.1202. Each copper?ion is coordinated by two bridging bidentate benzoate and 4 dimethylamine pyridine to form dimeric molecule. CCDC: 188744.展开更多
文摘The quantum chemical investigations of some representative bis-adducts of C60, C60O2, C60（NH）2, C60（CH2NHCH2）2 and C60（SO4）2 have been carried out at the AM1 and PM3 semi-empirical molecular orbital levels. The relative energies of various isomers of these C60 bis-adducts have been calculated. For C60O2 and C60（NH）2 with the sterically non-demanding addends, cis-1 isomer resulted from 1,2-additions to adjacent 6/6 ring fusion is the lowest energy structure; for C60（CH2NHCH2）2 and C60（SO4）2 with sterically demanding addends, the most energetically preferred structure is e isomer. This is consistent with and enhances the general rule for regio-selectivity of fullerene C60 established by Hirsch, though Hirschs rule is summarized on the basis of methanofullerenes. The thermodynamic analysis is not significant to explain the experimentally observed regiochemistry for C60 bis-adducts, and the kinetic reasons or mechanisms may dominant in determining the regioselectivity of fullerene bis-adducts. Further addition patterns for multiple addition were also discussed.
文摘At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and 4 dimethylamine pyridine which affords the last products as binuclear copper?complex (1), [Cu(C6H5COO)2(C7H10N2)]2. This complex is further characterized by spectroscopic methods. The structure of complex (1) has been determined by a single crystal X ray analysis. Crystallographic data are as follows: monoclinic, space group P21/n, a=10.446(2)?, b=11.140(5)?, c=17.179(3)?, β=95.92(3)°, V=1988.4(7)?3, Z=4, F(000)=884, μ=11.27cm-1, D(calcd.)=1.429g·cm-3, R=0.0399, Rw=0.1202. Each copper?ion is coordinated by two bridging bidentate benzoate and 4 dimethylamine pyridine to form dimeric molecule. CCDC: 188744.
