Issue 45, 2022

Reassessment of N2 activation by low-valent Ti-amide complexes: a remarkable side-on bridged bis-N2 adduct is actually an arene adduct

Abstract

The complex {(TMEDA)2Li}{[Ti(N(TMS)2)2]2(μ-η22-N2)2} (5-Li) is the only transition metal N2 complex ever reported with two side-on N2 adducts. In this report, the similarity of 5-Li to a new inverse sandwich toluene adduct {(PhMe)K}{[Ti(N(TMS)2)2]2(μ-PhMe)} (6-K) necessitated a re-examination of the structure of 5-Li. Through a reassessment of the original disordered crystal data of 5-Li and new independent syntheses brought about through revisitation of the original reaction conditions, 5-Li has been re-assigned as an inverse sandwich toluene adduct, {(TMEDA)2Li}{[Ti(N(TMS)2)2]2(μ-PhMe)} (6-Li). The original crystal data could be fitted almost equally well to structural solutions as either 5-Li or 6-Li, and this study highlights the importance of a holistic examination of modeled data and the need for secondary/complementary analytical methods in paramagnetic inorganic syntheses, especially when presenting unique and unexpected results. In addition, further examination of reduction reactions of Ti[N(TMS)2]3 and [(TMS)2N]2TiCl(THF) in the presence of KC8 revealed rich solvent- and counterion-dependent chemistry, including several degrees of N2 activation (bridging nitride complexes, terminal bridging N2 complexes) as well as ligand C–H activation.

Graphical abstract: Reassessment of N2 activation by low-valent Ti-amide complexes: a remarkable side-on bridged bis-N2 adduct is actually an arene adduct

Supplementary files

Article information

Article type
Edge Article
Submitted
05 8 2022
Accepted
13 10 2022
First published
14 10 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 13330-13337

Reassessment of N2 activation by low-valent Ti-amide complexes: a remarkable side-on bridged bis-N2 adduct is actually an arene adduct

D. N. Huh, R. F. Koby, Z. E. Stuart, R. J. Dunscomb, N. D. Schley and I. A. Tonks, Chem. Sci., 2022, 13, 13330 DOI: 10.1039/D2SC04368H

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