Synthesis, Bonding and Properties of Conjugated Transition- Metal Complexes and Polymers

匹兹堡大学的霍普金斯教授将 合成具有共轭键过渡金属化合物 系统的支持下，从无机，生物无机，和 有机化学课程。 这些化合物将 结合一系列键以实现该目的， 包括金属-金属δ键、金属-配体π键，和 配体π键。 在大多数化合物中， 将是钼和钨，并且配体将包括 膦、亚烷基、亚烷基炔和桥连二烯。 的 待合成的化合物将包括两种单体物质 以及聚合物。 结合作用的评估 将通过低温电子光谱，核磁共振， 光谱学、X射线衍射和共振拉曼 谱 一些化合物将被研究 因为它们的非线性光学性质。 这项研究将 产生一个广泛的比较的影响共轭 在无机和它们的经典有机类似物中。 %%% 有机化学中的一个基本概念是共轭， 也就是说，单键和多键交替的影响。 共轭对有机物的性质有重要影响 分子。 本研究将确定 这一概念可以应用于无机化学， 特别是金属原子是必需的化合物 参与者的结合。 金属原子具有更多样的 比碳原子的键合模式（包括“δ”键合）， 这提高了在这样的系统中缀合的可能性， 甚至比在有机物中发现的影响更深远。 系统. 目前的研究将需要综合 设计用于接合的化合物， 它们的结构和物理性质的测量。

Professor Hopkins, of the University of Pittsburgh, will synthesize transition-metal compounds having conjugated bonding systems with support from the Inorganic, Bioinorganic, and Organometallic Chemistry Program. These compounds will incorporate an array of bonds to achieve this objective, including metal-metal delta bonds, metal-ligand pi bonds, and ligand pi bonds. In most of the compounds the metal centers will be molybdenum and tungsten, and the ligands will include phosphines, alkylidenes, alkylidynes, and bridging dienes. The compounds to be synthesized will include both monomeric species as well as polymers. Assessments of the effects of conjugation will be made by low-temperature electronic spectroscopy, NMR spectroscopy, X-ray diffraction, and resonance Raman spectroscopy. A number of the compounds will be investigated for their nonlinear optical properties. The research will generate an extensive comparison of the effects of conjugation in inorganic and their classic organic analogues. %%% A fundamental concept in organic chemistry is conjugation, i.e., the effects of alternating single and multiple bonds. Conjugation has major effects on the properties of organic molecules. The present study will determine the degree to which this concept can be applied to inorganic chemistry, and in particular to compounds where metal atoms are essential participants in the conjugation. Metal atoms have more diverse modes of bonding than carbon atoms (including "delta" bonding), which raises the potential for conjugation in such systems to have even more profound effects than are found in organic systems. The present research will entail the synthesis of compounds designed to engage in conjugation, the elucidation of their structures, and measurements of their physical properties.