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Evaluation of the Oxygen pi-Donation in Permethyltitanocene Silanolates and Alcoholates.

Publication at Faculty of Science |
2009

Abstract

A series of compounds [Cp*Ti-2(III)OR'] where R' is (Pr3Si)-Pr-i (2), Ph3Si (3), ((BuO)-Bu-t)(3)Si (4), (c-C5H9)(7)Si8O12 (5), and Bu-t (6) were prepared by protolysis of the titanium-methylene bond in singly tucked-in permethyltitanocene [Cp*Ti(III)(eta(5):eta(1)-C5Me4CH2)] with the respective silanols or tert-butanol. Their electronic transitions from the ground-state molecules to their first excited states (dominantly a 1a(1) -> b(2) transition) occur in the range 1300-1800 nm, originating from pi-donation from oxygen lone pair electrons to the Ti-O bond (as found by Andersen et al.

J. Am.

Chem. Soc. 1996, 118, 1719).