Issue 67, 2023

A mononuclear, terminal titanium(iii) imido

Abstract

We report the first mononuclear TiIII complex possessing a terminal imido ligand. Complex [TptBu,MeTi{[triple bond, length as m-dash]NSi(CH3)3}(THF)] (2) (TptBu,Me = hydridotris(3-tert-butyl-5-methylpyrazol-1-yl)borate) is prepared by reduction of [TptBu,MeTi{[triple bond, length as m-dash]NSi(CH3)3}(Cl)] (1) with KC8 in high yield. The connectivity and metalloradical nature of 2 were confirmed by single crystal X-ray diffraction studies, Q- and X-band EPR, UV-Vis and 1H NMR spectroscopies. The d1 complex [(TptBu,Me)TiCl(OEt2)][B(C6F5)4] (3), was prepared to spectroscopically compare it to 2. Electrochemical studies of 1 and 2 reveal a reversible 1e process, and chemical oxidants ClCPh3 or 1/2 eq. XeF2 react cleanly with 2 yielding 1 or the fluoride derivative [TptBu,MeTi{[triple bond, length as m-dash]NSi(CH3)3}(F)] (4), respectively.

Graphical abstract: A mononuclear, terminal titanium(iii) imido

Supplementary files

Article information

Article type
Communication
Submitted
11 Apr 2023
Accepted
20 Jun 2023
First published
21 Jun 2023

Chem. Commun., 2023,59, 10101-10104

Author version available

A mononuclear, terminal titanium(III) imido

J. S. Mohar, A. Reinholdt, T. M. Keller, P. J. Carroll, J. Telser and D. J. Mindiola, Chem. Commun., 2023, 59, 10101 DOI: 10.1039/D3CC01758C

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