Symmetrical Metal Alkoxides and Amides: Reactivity and Structural Studies

爱荷华州立大学的John Verkade教授将在无机、生物无机和有机金属项目的支持下研究“atrane”配位化合物。这些都是高度对称的化合物，具有多环烷氧基和酰胺类配体。一类化合物将金属中心置于带有轴胺的C3V环境中。另一类将类似，但与C2v(准四重)环境。过渡金属和主族金属中心都将使用。最初的研究将集中在这些有趣物种的合成上。Verkade还将对它们的金属迁移、轴向配体位移和其他反应进行机理研究。将采用的一种不寻常的技术是119Sn51V和73Ge核磁共振波谱。Atrans是一类有趣的化合物，其中一个中心金属原子对称地与平面上的三个或四个氧原子结合，而一个氮原子则轴向结合。在这类化合物中，中心金属可以系统地变化，分子的其他特征也可以变化。它们的高度对称性使它们具有高挥发性，这为中心金属原子的运输提供了一种不同寻常的机制。这类化合物的合成以及对其反应性的研究是本赠款的主题。

Professor John Verkade of Iowa State University will investigate "atrane" coordination compounds with support from the Inorganic, Bioinorganic, and Organometallic Program. These are highly symmetrical compounds with polycyclic alkoxide and amide-type ligands. One class of compounds will place the metal center in a C3v environment with an axial amine. The other class will be similar, but with a C2v (quasi-fourfold) environment. Both transition metal and main-group metal centers will be used. The initial studies will focus on synthesis of these interesting species. Verkade will also conduct mechanistic studies of their transmetallations, axial ligand displacements, and other reactions. An unusual technique to be employed will be 119Sn, 51V, and 73Ge NMR spectroscopy. %%% "Atranes" are an interesting class of compounds in which a central metal atom is bound symmetrically to three or four oxygen atoms in a plane, while a nitrogen atom is bound axially. In such compounds the central metal can be systematically varied, as can other features of the molecules. Their high symmetry endows them with high volatility, which provides an unusual mechanism for transporting the central metal atom. The synthesis of such compounds, as well as a study of their reactivity is the subject of the present grant.