Structure of the Trinuclear Titanium (IV) Alkoxides
Structure of the Trinuclear Titanium (IV) Alkoxides
复制标题
三核钛（IV）醇盐的结构
作者：
R. L. Martin;G. Winter
Caughlan等人于1951年12月首次建立了正钛酸的n-烷氧基衍生物的缔合。在冷冻苯中分子量的冰点测定显示，Ti（OC 2 H 5）4、Ti（OC 3 H 7）4和Ti（OC 4 H 9）4都是三聚体，除了在非常高的稀释度下观察到解离成单体。这种关联被归因于四价钛强烈倾向于获得六共价氧环境，例如在金红石或金红石中。Caughlan等人提出，如果每对钛原子由三个桥连烷氧基支撑，则可以实现这一点，从而产生两种替代结构I和II，其基于三个TiO 6-八面体的面对面堆叠。结构II需要一个四配位的正方形平面氧原子与三个钛原子和一个烷基相连，因此我们认为这是站不住脚的。
THE association of n-alkoxy derivatives of orthotitanic acid was first established as recently as December 1951 by Caughlan et al.1. Cryoscopic determinations of molecular weight in freezing benzene revealed that Ti(OC2H5)4, Ti(OC3H7)4 and Ti(OC4H9)4 were all trimeric except at very high dilutions when dissociation to the monomer was observed. The association was ascribed to the strong tendency of quadrivalent titanium to attain a six-covalent oxygen environment, as, for example, in rutile or anatase. Caughlan et al. suggested that this could be achieved if each pair of titanium atoms was supported by three bridging alkoxy-groups giving two alternative structures I and II, which were based on the stacking of three TiO6-octahedra face to face. Structure II necessitates a four-co-ordinated square planar oxygen atom attached to three titanium atoms and one alkyl group, and for this reason is considered by us to be untenable.