中国金属有机化学的进展

本文综述了中国金属有机化学的进展。第一部分是主族元素金属有机化学,它包括有机硅、硼、砷和锡的化学。第二部分是过渡金属有机化学,包括过渡金属有机络合物的合成、结构和反应;过渡金属有机络合物在有机合成中的应用;均相催化和小分子活化。综述引用文献383篇。     

含膦配体的铂羰基配合物催化苯的光羰化反应

采用“原位反应”的方法,研究了配合物Ｐｔ（ＰＭｅ３）２（ＣＯ）２和Ｐｔ（ｄｉｐｈｏｓ）（ＣＯ）２（ｄｉｐｈｏｓ：１,２－二（二特丁基膦）乙烷,即ｄ（ｔ－Ｂｕ）Ｐｅ,１,２－二（二环己基膦）乙烷,即ｄＣｙｈＰｅ;１,２－二（二环戊基膦）乙烷,即ｄＣｙｐＰｅ;１,２－二（苯基特丁基膦）乙烷,即Ｐｈ（ｔ－Ｂｕ）Ｐｅ）在室温和压下对苯的光羰化反应性能,得到了预期的反应产物苯甲醛和苯甲醇。它们均经色－质分析     

漫谈金属有机化学

引言金属有机化学和配位化学分别是从有机化学和无机化学两个领域中发展起来而又密切联系的学科,目前已汇成一股洪流,成为近代化学前沿领域之一.它的发展打破了传统的有机化学和无机化学的界限,金属有机化学已成为有机化学中主流之一,它的发展又与理论化学、合成化学、催化、结构化学、生物无机化学、高分子科学等交织在一起. 什么是金属有机化合物?凡是化合物中含有碳-金属键的都是金属有机化合物.不言而喻,根据我国化学名词命名法,凡有金字偏旁的元素与碳成键的化合物,当然属于金属有     

三核过渡金属配合物在催化反应中的研究进展

多核过渡金属配合物作为一类广泛应用的均相催化剂,其设计灵感往往来自天然酶的多金属活性位点所发挥的重要作用.目前,三核金属配合物作为活化小分子的多金属催化剂受到了广泛的关注.为深入理解三核过渡金属配合物在催化反应中作用特点,对近年报道的代表性三核过渡金属配合物按金属中心进行分类,并对配体环境形成特点及催化应用进行综述.从金属中心出发,讨论了三核过渡金属配合物的几何结构和电子特征;从配体环境出发,总结了关联三个独立的金属位点的配位环境特征;在催化应用方面,重点综述了三核过渡金属配合物在涉及特定化学键活化反应的催化作用机制,最后对三核过渡金属配合物的催化应用前景进行展望.     

表面有机化金属化学（Ⅰ）

阐述评述了表面有机金属化学形成和发展的前景、有机金属化合物与固体表面反应的基本规律和表面有机金属配合物的结构,对表面有机金属化学与催化化学的本质联系进行了讨论。     

富勒烯的金属配合物及其催化性能

富勒烯的金属配合物及其催化性能１）刘英陈远荫２）盛蓉生（武汉大学化学系武汉４３００７２）关键词富勒烯金属配合物催化分类号Ｏ６４３．３２碳元素的第三种存在形式富勒烯正以其独特的结构和性能以及诱人的应用前景引起人们日益浓厚的兴趣．其中又以Ｃ６０的研究为主...     

离子型膦配体及其离子型过渡金属配合物的合成和均相催化作用

与传统中性叔膦配体构建的过渡金属配合物相比,由离子型膦配体配位构建的过渡金属配合物具有典型的离子盐组成特点、独特的电子效应和几何构型。该类配合物中,不仅存在金属和配体间的配位作用,还存在正电荷的强吸电子效应和阴阳离子的静电作用,由此可以产生独特的催化性能。近年来,离子型过渡金属配合物的合成及其均相催化应用成为配位化学和均相催化研究中备受关注的领域。离子型过渡金属配合物的离子盐结构,使其在与室温离子液体溶剂结合使用时,离子型离子配体及其配合物能够严格被锁定在离子液体相,具有避免离子型离子配体及其配合物的流失、抑制其失活、并实现循环使用的优点,也成为均相催化固载化的绿色方法之一。本文综述了近十年发展的一类咪唑鎓基与膦配体中的磷原子毗邻的离子型膦配体的合成,及其相应Rh、Pd、Ru、Pt、Au、Ni、Cu等离子型配合物的构建,并介绍了它们在均相催化反应中的应用。     

表面有机金属化学(Ⅰ)

简要评述了表面有机金属化学形成和发展的背景、有机金属化合物与固体表面反应的基本规律和表面有机金属配合物的结构.对表面有机金属化学与催化化学的本质联系进行了讨论.     

环戊二烯基钌配合物催化的高选择性苯乙炔二聚反应

Transition metal vinylidene complexes (M=C=CHR) have attracted a great deal of attention in recent years as a new type of organometallic intermediates that may have unusual reactivity[1]. Their reactivity has been explored and their application to organic synthesis is developed[2]. Recent reports on the ruthenium-vinylidene complexes[3]suggest that the reaction of ruthenium-vinylidene complexes with a base generates the coordinatively unsaturated ruthenium acetylide species, which are involved in a number of catalytic and stoichiometric reactions of alkynes. For example,the coordinatively unsaturated ruthenium acetylide species C5Me5Ru(PPh3)-C≡CPh,formed from the reaction of the vinylidene complex C5Me5Ru(PPh3) (Cl)=C=CHPh with a base was reactive toward a variety of small molecules and active in catalytic dimerization of terminal alkynes[4]. The dimerization of terminal alkyne is an effective method of forming enynes, but its synthetic application in organic synthesis has been limited dueto low selectivity for dimeric products[5]. In this communication, we report that three ruthenium complexes were used as catalysts for the highly selective dimerization of phenylacetylene.     

金属有机化学中的绿色化学反应进展

着重综述了金属有机化学领域中所涉及的与绿色化学概念有关的一些化学反应,如水相反应、超临界流体及离子液体中的反应、固态反应、原子经济性及过渡金属催化的有机反应。     

Large Isotope Effects in Organometallic Chemistry

The kinetic isotope effect (KIE) is key to understanding reaction mechanisms in many areas of chemistry and chemical biology, including organometallic chemistry. This ratio of rate constants, k_H/k_D, typically falls between 1–7. However, KIEs up to 105 have been reported, and can even be so large that reactivity with deuterium is unobserved. We collect here examples of large KIEs across organometallic chemistry, in catalytic and stoichiometric reactions, along with their mechanistic interpretations. Large KIEs occur in proton transfer reactions such as protonation of organometallic complexes and clusters, protonolysis of metal–carbon bonds, and dihydrogen reactivity. C−H activation reactions with large KIEs occur with late and early transition metals, photogenerated intermediates, and abstraction by metal-oxo complexes. We categorize the mechanistic interpretations of large KIEs into the following three types: (a) proton tunneling, (b) compound effects from multiple steps, and (c) semi-classical effects on a single step. This comprehensive collection of large KIEs in organometallics provides context for future mechanistic interpretation.     

主族金属有机超分子化学进展

以有机主族金属化合物为基本单元进行的超分子自组装是近年来超分子化学的研究方向之一。本文主要对6种主族p区重金属(铟、铊、锡、铅、锑及铋)的典型有机金属超分子的自组装进行探讨和总结。     

沸石表面有机金属化学ZSM-5外表面上

用气体分析及IR,NMR和元素分析等方法研究了真空系统中230和280℃下四丁基锗在ZSM-5沸石表面上的接枝反应,并对所得沸石的热稳定性和吸附性质进行了表征.与作者曾报道的在硅胶及丝光沸石上的反应类似,四丁基锗也能与ZSM-5沸石表面上的硅羟基发生缩合反应,在其外表面或孔口生成组成为(≡Si—O)     

Two-State Reactivity in Organometallic Gas-Phase Ion Chemistry

In contrast to organic reactions, which can almost always be described in terms of a single multiplicity, in organometallic systems, quite often more than one state may be involved. The phenomenon of two states of different multiplicities that determine the minimum-energy pathway of a reaction is classified as two-state reactivity (TSR). As an example, the ion/molecule reactions of ‘bare’ transition-metal-monoxide cations with dihydrogen and hydrocarbons have been analyzed in terms of the corresponding potential-energy hypersurfaces. It turns out that, besides classical factors, such as the barrier heights, the spin-orbit coupling factor is essential, since curve crossing between the high- and low-spin states constitutes a distinct mechanistic step along the reaction coordinates. Thus, TSR may evolve as a new paradigm for describing the chemistry of coordinatively unsaturated transition-metal complexes. This concept may contribute to the understanding of organometallic chemistry in general and for the development of oxidation catalysts in particular.     

XXth International Conference on Organometallic Chemistry

Russian Journal of Organic Chemistry -     

First Journal of Organometallic Chemistry Conference

Anläßlich des 75. Geburtstags von Ernst Otto Fischer fand in München am 4. und 5. November die “First Journal of Organometallic Chemistry Conference” statt. Ein hochkarätiges Vortragsprogramm und über 170 Posterpräsentationen boten einen Überblick über aktuelle Forschungsthemen der metallorganischen Chemie.