Results of researches on study of the kinetics and isomerization mechanism of the alkyladamantanes in the presence of the heterogeneous catalysts of the acid type are considered as detection and experimental proof of ...Results of researches on study of the kinetics and isomerization mechanism of the alkyladamantanes in the presence of the heterogeneous catalysts of the acid type are considered as detection and experimental proof of a new intramolecular rearrangement of the carbcations bridged alicyclic hydrocarbons--2,4-moving of the methyl groups （β-methyl shift）. The proof of realization of such rearrangement is direct and primary formation 1,4-dimethyladamantane from 1,2-dimethyladamatane, passing a formation stage of the thermodynamic much stable 1,3-dimethyladamantane; direct formation 1,3,6-trimethyladamantane from 1,3,4-trimethyladamantane, excepting a formation stage 1,3.5-trimethyladamantane, and also other isomers which formation is impossible to explain by means of known 1,2-methyl shift （a-methyl shift）.展开更多
The intramolecular acetate rearrangement of the aminocarboxylate metal chelates with the hexdentate-coordinate has been investigated by dynamic NMR in recent years. However, the intramolecular processes of the metal q...The intramolecular acetate rearrangement of the aminocarboxylate metal chelates with the hexdentate-coordinate has been investigated by dynamic NMR in recent years. However, the intramolecular processes of the metal quinquedentate chelates have not been studied up to now. Here is reported the configurational reversion展开更多
A new type of intramolecular electrophilic rearrangements involving the shift of alkoxycarbonyl or acetyl groups from a carbon atom to an N-anionic center is presented.
The stereochemical nonrigidity of RfCo（PF3）x（CO）4-x（Rf=CF3,C2F5,C3F7,x=0-4） was studied at the theoretical level of B3LYP/6-31 1＋G^＊ via Gaussian 09.The intramolecular rearrangements in these penta-coordinated...The stereochemical nonrigidity of RfCo（PF3）x（CO）4-x（Rf=CF3,C2F5,C3F7,x=0-4） was studied at the theoretical level of B3LYP/6-31 1＋G^＊ via Gaussian 09.The intramolecular rearrangements in these penta-coordinated compounds are mainly caused by the vibrations of perfluoroalkyl groups.All the barriers along the reaction coordinate are less than 66.9 kJ/mol,which indicates that the rearrangements are kinetically favorable and hard to elucidate by experiment.Besides,ligand PF3 is a ligand similar to CO,the energy difference between the reactant and product is small.展开更多
文摘Results of researches on study of the kinetics and isomerization mechanism of the alkyladamantanes in the presence of the heterogeneous catalysts of the acid type are considered as detection and experimental proof of a new intramolecular rearrangement of the carbcations bridged alicyclic hydrocarbons--2,4-moving of the methyl groups （β-methyl shift）. The proof of realization of such rearrangement is direct and primary formation 1,4-dimethyladamantane from 1,2-dimethyladamatane, passing a formation stage of the thermodynamic much stable 1,3-dimethyladamantane; direct formation 1,3,6-trimethyladamantane from 1,3,4-trimethyladamantane, excepting a formation stage 1,3.5-trimethyladamantane, and also other isomers which formation is impossible to explain by means of known 1,2-methyl shift （a-methyl shift）.
基金Supported by the National Natural Science Foundation of China
文摘The intramolecular acetate rearrangement of the aminocarboxylate metal chelates with the hexdentate-coordinate has been investigated by dynamic NMR in recent years. However, the intramolecular processes of the metal quinquedentate chelates have not been studied up to now. Here is reported the configurational reversion
文摘A new type of intramolecular electrophilic rearrangements involving the shift of alkoxycarbonyl or acetyl groups from a carbon atom to an N-anionic center is presented.
文摘The stereochemical nonrigidity of RfCo（PF3）x（CO）4-x（Rf=CF3,C2F5,C3F7,x=0-4） was studied at the theoretical level of B3LYP/6-31 1＋G^＊ via Gaussian 09.The intramolecular rearrangements in these penta-coordinated compounds are mainly caused by the vibrations of perfluoroalkyl groups.All the barriers along the reaction coordinate are less than 66.9 kJ/mol,which indicates that the rearrangements are kinetically favorable and hard to elucidate by experiment.Besides,ligand PF3 is a ligand similar to CO,the energy difference between the reactant and product is small.
