Highly Reduced Organometallics of the Early Transition Elements

无机，生物无机和有机金属化学项目的目标是合成和表征含有过渡元素的有机金属化合物，这些过渡元素是以前未知的，极低氧化态的。在最近用环烷化钠还原金属卤化物合成含零价钛、锆和铪的羰基和有机膦化合物的基础上，将尝试合成钪、钇和4f块元素的第一批金属羰基化合物。这项研究的一个重要组成部分将是确定在4和4f组零价羰基和亚价羰基的合成和稳定中起重要作用的因素。还将审查除一氧化碳以外的潜在受体配体，例如烯烃、炔烃、共轭二烯和二氮的使用情况，以便更充分地评价低价早期过渡元素在化学合成中的潜力。该项目有望为化学合成提供强大的新试剂，并为以前只能通过金属原子蒸汽合成少量制备的材料提供新的途径。

The goal of this project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is the synthesis and characterization of organometallic compounds containing transition elements in previously unknown, extremely low oxidation states. Building on the recent synthesis of carbonyl and organophosphine compounds containing zerovalent titanium, zirconium and hafnium, prepared by reduction of metal halides with sodium napthenide, the synthesis of the first examples of metal carbonyls of scandium, yttrium and 4f block elements will be attempted. A significant component of the research will be to determine the factors which are important in the synthesis and stabilization of zero and subvalent carbonyls of the group 4 and 4f block elements. The use of potential acceptor ligands other than carbon monoxide, such as alkenes, alkynes, conjugated dienes and dinitrogen, will be examined also to assess more fully the potential of low-valent early transition elements in chemical synthesis. This project is expected to provide powerful new reagents for chemical synthesis, and to provide new routes to materials which previously could be prepared only in small amounts by metal atom vapor syntheses.