d^0过渡金属化合物对氧气反应性:合成和反应机理研究  

Reactivities of d^0 transition metal complexes toward oxygen:Synthetic and mechanistic studies

作　　者：陈树建 张欣豪[2] 林振阳[2] 吴云东[2] 薛子陵 

机构地区：[1]Department of Chemistry,The University of Tennessee,Knoxville [2]香港科技大学化学系

出　　处：《中国科学（B辑）》2009年第11期1296-1307,共12页Science in China(Series B)

基　　金：美国国家科学基金会(CHE-051692);香港研究资助局以及英国皇家学会Kan Tong Po客座教授计划资助

摘　　要：众所周知,过渡金属如卟啉中的铁与氧气的结合和反应对许多生物功能和催化氧化至关重要.在这些反应中,过渡金属一般含d价电子,并且金属被氧化往往是其中一个重要的反应步骤.近年来,氧气与d0过渡金属化合物如Hf(NR2)4(R=烷基)的反应被广泛用来制备金属氧化物薄膜以作为新型微电子器件中的栅(门)绝缘材料.这篇专题文章讨论我们近期对这些反应以及TiO2薄膜形成的研究.在许多氧气与dn过渡金属化合物的反应中,总是金属被氧化.然而,在d0过渡金属化合物如Hf(NMe2)4和Ta(NMe2)4(SiR3)与氧气的反应中通常是配体被氧化.如—NMe2和—SiR3配体分别形成了—ONMe2和—OSiR3配体.反应机理和理论方面的研究显示了微电子金属氧化物薄膜形成的途径.Transition metals such as Fe in porphyrin complexes are known to bind or react with O2, and such reactions are critical to many biological functions and catalytic oxidation using O2. The transition metals in these reactions often contain valence d electrons, and oxidation of metals is an important step. In recent years, reactions of O2 with do transition metal complexes such as Hf（NR2）4 （R = alkyl） have been used to make metal oxide thin films as insulating gate materials in new microelectronic devices. This feature article discusses our recent studies of such reactions and the formation of TiO2 thin films. In contrast to the reactions of many dn complexes where metals are often oxidized, reactions of do complexes such as Hf（NMe2）4 and Ta（NMe2）4（SiR3） with O2 usually lead to the oxidation of ligands, forming, e.g., --ONMe2 and --OSiR3 from --NMe2 and --SIR3 ligands, respectively. Mechanistic and theoretical studies of these reactions have revealed pathways in the formation of the metal oxide thin films as microelectronic materials.

关 键 词：氧气 氨基化合物 金属氧化 物栅(门)绝缘材料 理论研究 

分 类 号：O611.4[理学—无机化学]