Theoretical investigation of the reaction mechanism for formation of pyridinyl formimidamide ancillary ligand in the synthesis of a new class of iridium(III) complexes

Bain, NHAS, Mohd Ali, N, Robinson, D ORCID: https://orcid.org/0000-0003-2760-7163 and Abdel-Aal, A-BM, 2026. Theoretical investigation of the reaction mechanism for formation of pyridinyl formimidamide ancillary ligand in the synthesis of a new class of iridium(III) complexes. Journal of Organometallic Chemistry, 1043: 123903. ISSN 0022-328X

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Abstract

In this study, density functional theory (DFT) calculations were performed to explore the reaction mechanism for the formation of a silver-formimidamide intermediate complex in the synthesis pathway of a novel cyclometallated iridium(III) complex bearing a pyridine-formimidamide ancillary ligand. The purpose of this study is to provide a detailed explanation of how the cyclic carbene ancillary ligand of (2-(4-methylbenzyl)-1H-1,2,4-triazol-1-yl)pyridine, MBpyta converted into acyclic (E)-N-cyano-N-(4-methylbenzyl)-N'-(pyridin-2-yl) formimidamide, CNMBpyfa when undergoing complexation with chloro-bridged iridium(III) dimer [{Ir(F2ppy)2(µ-Cl)}2]. The calculated results showed that the role of silver(I) oxide and the electron-withdrawing effect of the starting ligand in reactants triggered the two stages of deprotonation of two carbons in the starting triazolium salt precursor. Geometrical optimization reveals that the crystal structure of complex Ir(F2ppy)2(CNMBpyfa) has the lowest electronic energy compared to other designated ancillary ligand positions, confirming that the experimental data represent the most stable state of the synthesized complex.

Item Type:	Journal article
Publication Title:	Journal of Organometallic Chemistry
Creators:	Bain, N.H.A.S., Mohd Ali, N., Robinson, D. and Abdel-Aal, A.-B.M.
Publisher:	Elsevier BV
Date:	1 January 2026
Volume:	1043
ISSN:	0022-328X
Identifiers:	Number Type 10.1016/j.jorganchem.2025.123903 DOI 2519089 Other
Rights:	©2025. This manuscript version is made available under the CC-BY-NC-ND 4.0 license https://creativecommons.org/licenses/by-nc-nd/4.0/
Divisions:	Schools > School of Science and Technology
Record created by:	Laura Borcherds
Date Added:	31 Oct 2025 15:02
Last Modified:	31 Oct 2025 15:02
URI:	https://irep.ntu.ac.uk/id/eprint/54650

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