Issue 42, 2023

New cationic coinage metal complexes featuring silyl group functionalized phosphine: syntheses, structures and catalytic studies in alkyne–azide cycloaddition reactions

Abstract

A series of coinage metal complexes bearing rarely explored ortho-silylated phosphine is reported. The treatment of diphenyl(2-(trimethylsilyl)phenyl)phosphine (1) with CuCl and [Cu(CH3CN)4]BF4 furnished the corresponding neutral [(1)CuCl]2 (2) and mono-cationic [(1)2Cu(CH3CN)]BF4 (3) complexes, respectively. The reactions of 1 with AgX (X = BF4, NO3) in 2 : 1 ratio furnished the corresponding mono cationic dicoordinate silver(I) complexes of the type [(1)2Ag]X (X = BF4 (4a), NO3 (4b)). The ortho-silylated phosphine ligand (1) was conveniently converted into the corresponding sulfide (5a) and selenide (5b) species, and their reactions with [Cu(CH3CN)4]BF4 yielded mono-cationic, homoleptic tris(silylphosphinochalcogenide)copper(I) complexes of the type [(5a/5b)3Cu]BF4 (6a/6b). The molecular structures of 2–4 and 6 were established by single-crystal X-ray diffraction analysis. The copper complexes 2, 3, and 6a were employed as catalysts in azide–alkyne cycloaddition reactions. Among these complexes, 3 was extensively used in the preparation of various mono- and bis-triazoles consisting of tolyl, benzyl, carbazolyl, and propargylic ether groups. Three sets of substituted triazole derivatives were achieved under mild conditions by employing copper(I) catalytic systems. The mechanistic studies indicated the formation of a heteroleptic copper(I) triazolide intermediate which was detected by high-resolution mass spectral analysis.

Graphical abstract: New cationic coinage metal complexes featuring silyl group functionalized phosphine: syntheses, structures and catalytic studies in alkyne–azide cycloaddition reactions

Supplementary files

Article information

Article type
Paper
Submitted
01 jun 2023
Accepted
11 set 2023
First published
12 set 2023
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2023,52, 15549-15561

New cationic coinage metal complexes featuring silyl group functionalized phosphine: syntheses, structures and catalytic studies in alkyne–azide cycloaddition reactions

A. K. Sahoo, A. Kumar Sahoo, B. Das, S. J. Panda, C. S. Purohit and A. Doddi, Dalton Trans., 2023, 52, 15549 DOI: 10.1039/D3DT01692G

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements