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Issue 31, 2018
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Carbodiphosphorane-based nickel pincer complexes and their (de)protonated analogues: dimerisation, ligand tautomers and proton affinities

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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

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Article information


Submitted
29 Dec 2017
Accepted
14 Feb 2018
First published
15 Feb 2018

Dalton Trans., 2018,47, 10544-10552
Article type
Paper

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

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