Issue 45, 2022

Towards new coordination modes of 1,2,3-triazolylidene: controlled by the nature of the 1st metalation in a heteroditopic bis-NHC ligand

Abstract

An unusual effect of the nature of the first metal coordination of a heteroditopic N-heterocyclic carbene ligand (L2) towards the coordination behavior of 1,2,3-tzNHC is explored. The first metal coordination at the ImNHC site (complexes 3 and 4) was noted to substantially influence the electronics of the 1,2,3-triazolium moiety leading to an unprecedented chemistry of this MIC donor. Along this line, the RhIII/IrIII-orthometalation in complexes 4 makes the triazolium C4–H more downfield shifted than C5–H, whereas a reverse trend, although to a lesser extent, is observed in the case of the non-chelated PdII-coordination. This difference in behavior assisted us to achieve the selective activation of triazole C4/C5 positions, not observed before, as supported by the isolation of the homo- and hetero-bimetallic complexes, 5, 6 and 7–9via C5- and C4-metalation, respectively. Furthermore, the %Vbur calculations eliminate any considerable steric influence and the DFT studies strongly support the selectivity observed during bimetalation.

Graphical abstract: Towards new coordination modes of 1,2,3-triazolylidene: controlled by the nature of the 1st metalation in a heteroditopic bis-NHC ligand

Supplementary files

Article information

Article type
Edge Article
Submitted
08 Sep 2022
Accepted
20 Oct 2022
First published
21 Oct 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, 13387-13392

Towards new coordination modes of 1,2,3-triazolylidene: controlled by the nature of the 1st metalation in a heteroditopic bis-NHC ligand

P. M. Illam, C. S. Tiwari and A. Rit, Chem. Sci., 2022, 13, 13387 DOI: 10.1039/D2SC05024B

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