Main Group Elements in Unusual Environments

今年的无机、生物无机和有机金属奖颁给了德克萨斯大学奥斯汀分校的Alan H. Cowley博士，以表彰他在合成含有主族元素的新型化合物方面所做的基础性工作。待研究的元素包括第15组的E = P、As、Sb、Bi和第13组的M = Al、Ga、In。本研究的目的是制备低配位数的RE片段（即膦烯、砷烯、甾烯和铋烯）和RM（四种电子类碳物质），并将这些片段整合到新的环、簇和聚合物中或作为配体使用。取代基R可以是甲基、乙基或多种体积较大的碳氢化合物。这些碎片将通过热、光化学或电化学消除氢、一氧化碳、二氧化碳或二硅烷及其较重的同系物而产生。该项目包括13族杂环的合成，作为ME片段潜在来源的13族和15族化合物的合成，类型（RMERR）n（其中n = 1-3）具有特殊几何形状的分子的构建，以及通过与过渡金属配位来稳定ME片段。制备含有铝、镓或铟以及磷、砷或锑的化合物可能会产生具有有趣的光学或电学性质的材料。这项研究的目标之一是将吸收光的不同类型的基团（发色团）附着在含有上述元素对的化合物上。这些基团的引入可以使这些或相关化合物在通过光辅助生长制造半导体中使用。由于扩散可能会减少并产生更尖锐的结，这将是目前热方法的理想替代方案。

This award in the Inorganic, Bioinorganic, and Organometallic Program is to Dr. Alan H. Cowley of the University of Texas at Austin for fundamental work on the synthesis of novel compounds containing main group elements. The elements to be studied include E = P, As, Sb, and Bi from group 15 and M = Al, Ga, and In from group 13. The goal of the research is to prepare low coordination number fragments of RE (i.e., phosphinidenes, arsinidenes, stibinidenes, and bismuthinidenes) and RM (four electron carbenoid species) and incorporate those fragments into novel rings, clusters, and polymers or use them as ligands. The substituent R may be methyl, ethyl, or a wide variety of bulky hydrocarbons. The fragments will be generated by thermal, photochemical or electrochemical elimination of hydrogen, carbon monoxide, carbon dioxide, or disilane and its heavier congeners. The project includes the synthesis of group 13 heterocycles, the synthesis of group 13 and group 15 compounds as potential sources of ME fragments, the construction of molecules of the type (RMERR)n, where n = 1-3, with unusual geometries, and the stabilization of ME fragments by coordination to transition metals. %%% Preparation of compounds containing aluminum, gallium, or indium together with phosphorus, arsenic or antimony may result in materials with interesting optical or electrical properties. One goal of this research is to attach different types of groups which absorb light (chromophores) to compounds containing the pairs of elements mentioned above. Introduction of such groups could enable use of these or related compounds in the manufacture of semiconductors by photo-assisted growth. Because diffusion might be reduced and sharper junctions produced, this would be a desirable alternative to present thermal methods.