Issue 31, 2018

Carbodiphosphorane-based nickel pincer complexes and their (de)protonated analogues: dimerisation, ligand tautomers and proton affinities

Abstract

The reactivity patterns of carbodiphosphoranes (CDPs) as ligands are much less explored than those of isoelectronic analogues. In the current manuscript, we investigate the reactivity of the carbodiphosphorane-based PCP nickel(II) pincer complex [({dppm}2C)NiCl]Cl (1) towards acids and bases, calculate proton affinities, analyse the bonding situation and tautomeric forms with the aim to evaluate whether CDPs can potentially act as cooperative ligands in catalysis (dppm = 1,1-bis(diphenylphosphino)methane). Our investigations show that different tautomeric forms are stable for the coordinated and the uncoordinated ligand. The protonated CDP-based complex 2 represents a rare example of a cationic donor group binding to a cationic metal centre. The continuous arm-deprotonation of 1 leads to the formation of remarkably stable dimers with Ni–C–P–C-metallacycles. In comparison to corresponding boron and amine-based ligands, the coordinated CDP-group exhibits the lowest proton affinity according to DFT calculations, indicating that coordinated CDP ligands can potentially serve as proton relay in cooperative catalysis.

Graphical abstract: Carbodiphosphorane-based nickel pincer complexes and their (de)protonated analogues: dimerisation, ligand tautomers and proton affinities

Supplementary files

Article information

Article type
Paper
Submitted
29 Dec. 2017
Accepted
14 Febr. 2018
First published
15 Febr. 2018

Dalton Trans., 2018,47, 10544-10552

Carbodiphosphorane-based nickel pincer complexes and their (de)protonated analogues: dimerisation, ligand tautomers and proton affinities

L. Maser, J. Herritsch and R. Langer, Dalton Trans., 2018, 47, 10544 DOI: 10.1039/C7DT04930G

To request permission to reproduce material from this article, 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 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