Imido-pyridine Ti(iv) compounds: synthesis of unusual imido–amido heterobimetallic derivatives?

Dalton Transactions Pub Date: 2015-05-07 DOI: 10.1039/C5DT01320H

Abstract

The reaction of lithiated picolines and [TiCl3(η5-C5Me5)] leads to several bridging or terminal imido compounds, each of which can be selectively formed by controlling the stoichiometry and temperature. Specifically, the dinuclear imido-bridged [TiCl(η5-C5Me5)(μ-NR)]2 (1a, NR = 2-imido-3-picoline; 1b, NR = 2-imido-5-picoline) species and the unusual Ti–Li imido–amido heterobimetallic complex [{Li(THF)}{Ti(η5-C5Me5)(NR)(NHR)2}] (2a, NR = 2-imido-3-picoline; 2b, NR = 2-imido-5-picoline) were isolated. Compounds 2 are in effect the first structurally characterized examples of titanium(IV) coordinated to terminal imido-pyridines. DFT-D calculations for 2a denote a multiple bond character between titanium and the imido ligand and a strong polarization of the electron density by the alkali cation in spite of the lack of intermetallic bonding.

Graphical abstract: Imido-pyridine Ti(iv) compounds: synthesis of unusual imido–amido heterobimetallic derivatives
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