Synthesis, Reactivity and Catalysis of Novel Metallacarboranes

无机、生物无机和有机金属奖授予加州大学洛杉矶分校化学系的M. Frederick Hawthorne博士。主要研究主族和镧系金属碳硼烷的合成、结构表征和反应性。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。这些化合物有望表现出不同寻常的结构和高反应活性。镧系碳硼烷的合成和表征将通过与卟啉或大环络合来克服。镧碳硼烷的烷基、氢化物和多氢化物配合物也将被合成。将制备新的In、Ge、Sn、Pb、P、As和Sb碳硼烷夹层配合物，以及Si、Ge、Sn、P和As的低价sigma键碳硼烷配合物。最后，碳硼烷阴离子将作为二烷基铝阳离子的载体。新合成的碳硼烷和金属碳硼烷有望表现出新的键合类型和反应活性。这些结果不仅将增加对主要基团和簇化合物的基本认识，而且将开发用于合成其他此类配合物的材料。当考虑到这些化合物在开发电子或聚合物材料方面的潜在效用时，它们就变得重要起来。此外，氢化物可能是活化C-H键的有效催化剂。

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.