A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted...A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted porphyrin. The influence of nitrate salts and complex metal ion to the reaction were investigated. The extent of 2\|nitration increased with the electronegativity of the central metal. When Cu(NO 3 ) 2 · 3H 2O was used as nitrating reagent, almost quantitative yields of 2\|nitro porphyrin were obtained in the case of Cu(Ⅱ) or Ni(Ⅱ) chelates, while Zn(Ⅱ) or Mn(Ⅲ) chelates gave 50% and 30% yields respectively. If Zn(NO 3 ) 2 ·10H 2 O was used as nitrating agent, no product was found for Cu(Ⅱ) or Ni(Ⅱ) chelates, 12% was found for Zn(Ⅱ) chelates. The other metal ion and nitrate salts were also found in quite different influence.展开更多
A mild,efficient and eco-friendly process for the electrophilic nitration is described using N_2O_5 as a green nitrating agent in the presence of rare earth metal triflates[RE（OTf）_3]under mild conditions.
The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline （phen） of general formula [Ln（phen）2（NO3）2（H2O）2]·NO3 （where, Ln=Ce, Pr and Nd） were prepared and characterized by X-...The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline （phen） of general formula [Ln（phen）2（NO3）2（H2O）2]·NO3 （where, Ln=Ce, Pr and Nd） were prepared and characterized by X-ray crystallography. Thermolysis of these complexes was investigated by simultaneous thermogravimetry （TG） and differential thermal analysis （DTA）. Isothermal TG was taken to evaluate the kinetic parameters using model fitting as well as model free isoconversional methods. The thermolytic pathways were also suggested, which involves decomposition followed by ignition. All the three complexes had coordination number ten and showed multistep decompositions. In order to evaluate the response of rapid heating, ignition delay （Di） measurements were undertaken. The activation energies for ignition were found to decrease in the order： Nd〉Pr〉Ce.展开更多
文摘A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted porphyrin. The influence of nitrate salts and complex metal ion to the reaction were investigated. The extent of 2\|nitration increased with the electronegativity of the central metal. When Cu(NO 3 ) 2 · 3H 2O was used as nitrating reagent, almost quantitative yields of 2\|nitro porphyrin were obtained in the case of Cu(Ⅱ) or Ni(Ⅱ) chelates, while Zn(Ⅱ) or Mn(Ⅲ) chelates gave 50% and 30% yields respectively. If Zn(NO 3 ) 2 ·10H 2 O was used as nitrating agent, no product was found for Cu(Ⅱ) or Ni(Ⅱ) chelates, 12% was found for Zn(Ⅱ) chelates. The other metal ion and nitrate salts were also found in quite different influence.
基金the financial support from the National Nature Science Foundation of China Academy of Engineering Physics(No.10976014)Nature Science Foundation of Jiangsu Province(No.BK2011697)
文摘A mild,efficient and eco-friendly process for the electrophilic nitration is described using N_2O_5 as a green nitrating agent in the presence of rare earth metal triflates[RE（OTf）_3]under mild conditions.
文摘The nitrate complexes of cerium, praseodymium and neodymium with 1,10-phenanthroline （phen） of general formula [Ln（phen）2（NO3）2（H2O）2]·NO3 （where, Ln=Ce, Pr and Nd） were prepared and characterized by X-ray crystallography. Thermolysis of these complexes was investigated by simultaneous thermogravimetry （TG） and differential thermal analysis （DTA）. Isothermal TG was taken to evaluate the kinetic parameters using model fitting as well as model free isoconversional methods. The thermolytic pathways were also suggested, which involves decomposition followed by ignition. All the three complexes had coordination number ten and showed multistep decompositions. In order to evaluate the response of rapid heating, ignition delay （Di） measurements were undertaken. The activation energies for ignition were found to decrease in the order： Nd〉Pr〉Ce.
