Structural, Chemical, and Bonding Studies of Electron Deficient Boron Halide Clusters

这个无机、生物无机和有机金属项目的奖项支持伊利诺伊大学芝加哥分校化学系的John A. Morrison博士关于多面体卤化硼簇的研究。将合成具有相等数目(n)的硼和卤化物原子（包括n = 7,8,10,11,12）的二价阴离子，并使用PES， XPS， NMR和x射线晶体学表征其反应性和结构。四卤化二硼、四卤化四硼和B(14)Cl（18）也将进行研究。取代基不仅限于卤化物，还包括烷基、醇氧基和酰胺基。本研究的目的是研究这些缺电子化合物的键合模式，这些化合物有望呈现出以前在硼簇中未观察到的结构。分子轨道计算有助于解释光谱和成键。含有多达12个硼原子的大型规则多面体团簇是众所周知的。每个硼通常还与一个氢或卤化物原子相连。将团簇保持在一起所需的“框架”电子的数量通常是2n+2，其中n是团簇中硼原子的数量。Morrison将合成仅含有2n个电子的新物种，并观察其对簇的形状和反应性及其成键特性的影响。虽然这项研究是基础性的，但它可能适用于其他元素的簇，特别是那些在许多催化和电子材料中发现的含有金属的元素簇。

This award in the Inorganic, Bioinorganic, and Organometallic Program supports research by Dr. John A. Morrison of the Chemistry Department, University of Illinois at Chicago, concerning polyhedral boron halide clusters. Divalent anions with equivalent numbers (n) of boron and halide atoms (including n = 7, 8, 10, 11, 12) will be synthesized and their reactivities and structures characterized using PES, XPS, NMR, and X-ray crystallography. Diboron tetrahalides and tetraboron tetrahalides and B(14)Cl(18) will also be studied. Substituents will not be limited to halides, but also will include alkyl, alkoxide, and amide groups. The goal of the research is to investigate the bonding modes of these electron deficient compounds which are expected to exhibit structures not previously observed in boron clusters. Molecular orbital calculations will facilitate the interpretation of spectra and bonding. %%% Large regular polyhedral clusters containing up to 12 boron atoms are well known. Each boron is typically bound also to a hydrogen or halide atom. The number of "framework" electrons required to hold the cluster together is usually 2n+2, where n is the number of boron atoms in the cluster. Morrison will synthesize novel species which contain only 2n electrons and observe the effects on the shape and reactivity of the cluster and its bonding characteristics. Although the research is fundamental, it may be applicable to clusters of other elements, particularly those containing metals which are found in many catalytic and electronic materials.