Enantiopure pseudo-C3-symmetric titanium alkoxide with propeller-like chirality.

An enantiopure amine tris(phenolate) ligand containing a single stereogenic center has been used to control the propeller-like chirality of a derived pseudo-C3-symmetric titanium isopropoxide complex with excellent levels of diastereocontrol. [structure: see text].

Bis(bismuth)toluene inverted-sandwich complex supported by aminetris(phenoxide) ligands.

The reaction of bismuth amides or alkoxides with phenolic ligand precursors yields Bi complexes of aminetris(phenoxide)s, one of which was characterized by X-ray crystallography, revealing monomeric Bi units of the tetradentate NO3 ligand further associated via a symmetrical toluene bridge into a bis(bismuth)toluene inverted-sandwich complex. Synthesis of the analogous Sb complex suggests a markedly different geometric and electronic environment at the metal center, as evidenced by the solid-state molecular structure. Density functional theory calculations of the sandwich bismuth arene complex indicate the presence of a weak sigma*-2pi interaction.

Facile resolution of constrained geometry indenyl-phenoxide ligation.

The 2-(inden-3-yl)phenoxide ligand can be resolved at both tetrahedral and octahedral Group 4 metal centers using chiral binaphthoxide ligands.