劈开组合法合成新结构和新成键的金属羰基簇合衍生物

The Syntheses of Metal Carbonyl Cluster Derivatives Containing Novel Structural Types and New Bonding Models by a Cleavage and Combination Method

介绍了一种独特而有效的合成新结构和新成键的金属簇合物的“劈开组合法”：利用含有多种可配原子（Ｃ、Ｎ或Ｐ、Ｓ）的前配体与二元金属羰合物的反应，前配体在不同位点的劈开，提供多样化的分子片充当各种配体，与金属羰合物组建生成各种新结构和新成键的三至七核的金属羰基簇合衍生物，由此得到一系列新型的含端卡宾碳配位基和二齿桥基的三核铁或钴簇，以及多种罕见的含半填隙磷原子和复杂含磷硫桥基的六核和七核钴簇．它们当中，许多以结构奇特、成键新颖、配体复杂为特色，扩展了原子簇化合物的物种范围．同时探讨了某些合成反应的劈开组合过程及所生成新簇合物的几何结构和成键特征．其中一类Ｃｏ６簇是由一桥二组块三元件组装而成，表明“劈开组合法”与卢喜锡等提出的“活性元件组装法”合成原子簇化合物，在反应过程与簇骨架转化上具有密切关系．

It describes the so called “cleavage and combination method” which is special and effective for the syntheses of metal carbonyl cluster derivatives with novel structural types and new bonding models. The application of the cleavage in different point or site of the ligand precusors which containing a lot of potential coordination atoms (C、N or P、 S) to afford many kinds of the fragments and then during the reactios these fragments as ligands would combined with the binary metal carbonyls to yield the novel terminal carbene ligand and bidentate bridging ligand containing trinuclear iron or cobalt clusters, and a series of rare semi interstitial P atom and complicated phosphieo/thiolato bridging ligand containing Hexa and Hepta cobat clusters. The special features of these new compounds are with rare structures, with novel bondings and with unusal complicated ligands, indicating the expansion of the species and ranges of the cluster chemistry. It has discussed some “cleavage and combination” processes of the synthetic reactions and the unusual geometric structures and bonding modes of some new cluster compounds and we have found that there is a kind of Co 6 cluster which has demonstrated the unit combination approach between two building block units and a bridge unit. So, our “cleavage and combination method” and Lu Jiaxi′s unit construction approach has a tight connection on the synthesized process and the conversion of the cluster skeletons.