Synthesis, Reactivity and Catalysis of Novel Metallacarboranes

该奖项授予加州大学洛杉矶分校化学系M·弗雷德里克·霍桑博士。这项研究将主要集中在主族金属碳烷和稀土元素的合成、结构表征和反应活性方面。将包括对含有Mg、Sc、Y、La、Ce、Nd、Gd、Lu、Th和U的金属碳硼烷的研究。这些化合物有望显示出不寻常的结构和高的反应活性。通过将镧系元素与卟啉或大环络合，将克服合成和表征镧系碳硼烷的困难。还将合成稀土碳硼烷的烷基、氢化物和聚氢化物配合物。将制备新的In、Ge、Sn、Pb、P、As和Sb的碳硼烷三明治络合物，以及低价sigma键合的Si、Ge、锡、P和As的碳硼烷络合物。最后，碳硼烷阴离子将被用作二烷基铝阳离子的载体。%合成的新碳硼烷和金属碳硼烷物种有望表现出新型的成键和反应活性。这些结果不仅将增加对主族和簇合物的基本了解，而且还将开发用于合成这类额外络合物的材料。当考虑到它们在开发电子或聚合物材料方面的潜在用途时，这类化合物变得重要起来。此外，氢化物物种可能是C-H键活化的有效催化剂。

This award in the Inorganic, Bioinorganic, and Organometallic Program is made to Dr. M. Frederick Hawthorne of the Chemistry Department, University of California at Los Angeles. The research will focus primarily on the synthesis, structural characterization, and reactivity of metallacarboranes of main-group and lanthanide elements. Included will be studies of metallacarboranes incorporating Mg, Sc, Y, La, Ce, Nd, Gd, Lu, Th, and U. These compounds are expected to exhibit unusual structures and high reactivity. Difficulities in synthesizing and characterizing lanthanacarboranes will be overcome by complexing the lanthanide to porphyrins or macrocycles. Alkyl, hydride, and polyhydride complexes of the lanthanacarboranes will also be synthesized. New carborane sandwich complexes of In, Ge, Sn, Pb, P, As, and Sb will be prepared as will low-valent sigma-bonded carborane complexes of Si, Ge, Sn, P, and As. Finally, carborane anions will be used as supports for dialkylaluminum cations. %%% The new carborane and metallacarborane species synthesized are expected to exhibit new types of bonding and reactivity. Not only will the results increase fundamental understanding of main group and cluster compounds, but materials useful for the synthesis of additional complexes of this type will be developed. Such compounds gain importance when their potential utility for development of electronic or polymeric materials is considered. In addition, the hydride species may be effective catalysts for C-H bond activation.