Li3N、Mg3N2、Ca3N2催化作用的比较和分析

 Li₃N、Mg₃N₂和Ca₃N₂是高温高压下以hBN为原料合成cBN的催化剂。在实验中发现它们对常压高温下生成hBN的反应也表现出催化作用。对比了三种氮化物催化效果的差异，发现三种氮化物都只有在熔融状态下才能表现出催化效果，以及三种氮化物对生成hBN反应的催化效果与它们在高温高压下合成cBN反应的催化效果次序相似。提出了对合成hBN有催化作用的化合物也将对合成cBN表现出催化作用的观点。     

Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003     

A simplified green chemistry approach to the Biginelli reaction using ‘Grindstone Chemistry’

Grindstone Chemistry--a greatly evolved version of Toda’s method of grinding solids together for solvent-free chemical reactions--has been described and its usefulness illustrated by the successful application of this technique to a simplified process for conducting the multi-component Biginelli reaction for the synthesis of physiologically active tetrahydropyrimidinones.     

Rhodium-catalyzed addition of arylstannanes to carbon-heteroatom double bond

The addition of arylstannanes to the carbon-heteroatom double bond in the presence of a catalytic amount of a cationic rhodium complex ([Rh(cod)(MeCN)₂]BF₄) was examined. The reactions of aldehydes, α-dicarbonyl compounds, and N-substituted aldimines with the arylstannanes gave corresponding alcohols, α-hydroxy carbonyl compounds, and amines, respectively. An arylrhodium complex generated by the transmetalation with the arylstannane was probably the active catalytic species.     

Advances in late transition metal catalysts for olefin polymerization/oligomerizarion

In this review article, we have consolidated our recent studies on late transition metal catalysts (mainly Fe, Co) for olefin polymerization/oligomerization. A series of bisiminopyridyl Co(II) and Fe(II) complexes were synthesized. These catalysts when activated with MAO in aromatic or aliphatic hydrocarbon solvents, oligomerize or polymerize ethylene to α-olefins or high molecular weight polymers with exceptionally high activities and selectivities. The electronic and steric effects of allyloxy and benzyloxy substituted bisiminopyridyl Fe(II) and Co(II) complexes were also investigated. The influence of catalyst structure and temperature on the polymerization activity, thermal properties and molecular weight were discussed. The effects of heterogenization of these catalysts on silica and modified SBA-15 were analyzed. The polymerization of polar monomers such as vinyl ethers and methyl methacrylate was tested and no specific trends in activity and polymer molecular weight with changes in steric bulkiness around the metal center were observed with the same catalyst system.     

Selective double Suzuki cross-coupling reactions. Synthesis of unsymmetrical diaryl (or heteroaryl) methanes

Using a double Suzuki cross-coupling reaction ortho- or para-bromobenzyl bromides are easily transformed into unsymmetrical diaryl (or heteroaryl) methanes     

Application of polymer-supported triphenyl phosphine in the palladium-catalyzed cyanation reaction under microwave conditions

A variety of aryl nitriles were prepared in excellent yields from the palladium acetate catalyzed coupling of aryl halides with Zn(CN)₂ using polymer-supported triphenyl phosphine as the ligand and dimethylformamide as solvent under microwave irradiation conditions.     

Performance of various activators in ethylene polymerization based on an iron(II) catalyst system

Ethylisobutylaluminoxane (EBAO) and its analogues were synthesized by a reaction between an triethylaluminum (Et₃Al)/triisobutylaluminum (i‐Bu₃Al) mixture and 4‐fluorobenzeneboronic acid, phenylboronic acid, or n‐butaneboronic acid and subsequent hydrolysis with water. They were used as cocatalysts in ethylene polymerization catalyzed by an iron complex {[(ArN?C(Me))₂C₅H₃N]FeCl₂, where Ar is 2,6‐diisopropylphenyl}. Polyethylene with a high molecular weight and a narrow molecular weight distribution was prepared with modified EBAOs, and the performance of the iron complex at high polymerization temperatures was greatly improved. The activators for the iron complex also affected the polymerization activity and the molecular weight of the resultant polyethylene. It was suggested that the stereo and electronic effects of the substitute groups of aluminoxane contributed to the improved performance of the new activators. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1093–1099, 2004     

Novel Chiral Ferrocenyl Aziridino Alcohol Catalysts Promoting Asymmetric Addition of Diethylzinc to Aldehydes

Optically active aziridino alcohols containing ferrocenyl groups were prepared from commercially available L-threonine in excellent yields and used as catalysts to promote the asymmetric addition of diethylzinc to aryaldehydes to afford 1-arylpropanol in up to 84% enantiomeric excesses with moderate to good yields.     

Synthesis of new terpene derivatives via ruthenium catalysis: rearrangement of silylated enynes derived from terpenoids

Enyne rearrangement of silylated modified terpenoids has been used as the key step for the synthesis of new terpenes and terpenoids. The catalytic system generated in situ from [RuCl₂(p-cymene]₂, 1,3-bis(mesityl)imidazolinium chloride and cesium carbonate is able to perform the transformation of silylated 1,7-enynes into cyclic siloxanes. Selective cleavage of the silicon-carbon and silicon-oxygen bonds by simple reactions has been performed to afford new terpenes and terpenoids by formal addition of a C5 unit.