Driving Diverse Bond Functionalisation with N-Heterocyclic Silylene-Coinage Metal-Aryl Complexes

Abstract

Anchoring homolytic and heterolytic bond functionalisation at low-coordinate coinage metal centres is important due to their potential use as active catalysts in organic transformations. In the realm of carbene-stabilised coinage metal chemistry, heteroatom functionalised coinage metal precursors synthesised from such bond activations have long been explored. Interestingly, N-heterocyclic silylene, being equally potent neutral donor ligands, has not been used for the same. Of note, carbene-stabilised heteroatom functionalised coinage metal precursors are vastly developed with copper centres only, while silver has been underexplored. This work reports the isolation of a variety of [PhC{N(tBu)}2SiN(SiMe3)2] (1) coordinated aryl-copper(I) and aryl-silver(I) complexes (2-8). We have also examined the reactivity pattern of organo-copper with differently substituted silylenes (9-11). These complexes were then utilised to cleave various homolytic and heterolytic bonds to access silylene-coordinated heteroatom functionalised coinage metal complexes (12-24). We have shown the reaction of reactive aryl-coinage metal precursors towards homolytic bonds, having B–B and Se–Se bonds, which led to the formation of NHSi-supported dimeric µ-boryl bound Cu(I) complex (12) and a new class of unprecedented NHSi-supported coinage metal-selenogenolates (14-16). These aryl-coinage metal precursors also smoothly afforded several elusive NHSi-copper and silver amides (17-22) via N–H bond cleavage. A heterolytic cleavage of the P–Si bond resulted in the formation of NHSi stabilised copper and silver phosphide complexes (23 and 24), among which the latter is the first precedent of the dimeric Ag-phosphide complex. Lastly, we have utilised NHSi→copper–aryl complexes as aryl transfer reagents in C–C coupling reactions, which led to the formation of products in excellent yields with high TON. The analogous silver complex was employed in the three-component α-aminonitrile synthesis efficiently. Our report establishes that NHSi coordinated aryl copper and silver complexes as the perfect and robust platform for accessing a diverse array of reactive coinage metal precursors that were hitherto unknown.

Supplementary files

Transparent peer review

To support increased transparency, we offer authors the option to publish the peer review history alongside their article.

View this article’s peer review history

Article information

Article type
Edge Article
Submitted
03 فرؤری 2025
Accepted
28 جوٗن 2025
First published
30 جوٗن 2025
This article is Open Access

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

Chem. Sci., 2025, Accepted Manuscript

Driving Diverse Bond Functionalisation with N-Heterocyclic Silylene-Coinage Metal-Aryl Complexes

M. Ghosh, K. Gaurav, P. Panwaria, R. Panday, S. Tothadi and S. Khan, Chem. Sci., 2025, Accepted Manuscript , DOI: 10.1039/D5SC00879D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements