Loading…

Theoretical insights into the electronic structure of nickel(0)-diphosphine-carbon dioxide complexes

•The asymmetric stretching frequency of the bound carbon dioxide is an appropriate descriptor as electronic parameter for the spectator phosphine ligand.•The coordination strength of the carbon dioxide ligand is sensitive to the basicity of the diphosphine but insensitive to the chelate ring size.•T...

Full description

Saved in:
Bibliographic Details
Published in:Journal of organometallic chemistry 2020-10, Vol.924, p.121462, Article 121462
Main Authors: Kégl, Tímea R., Carrilho, Rui M. B., Kégl, Tamás
Format: Article
Language:English
Subjects:
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:•The asymmetric stretching frequency of the bound carbon dioxide is an appropriate descriptor as electronic parameter for the spectator phosphine ligand.•The coordination strength of the carbon dioxide ligand is sensitive to the basicity of the diphosphine but insensitive to the chelate ring size.•The bond path between nickel and the coordinating oxygen only exists for strongly electron withdrawing phosphines. The coordination properties of carbon dioxide bound to Ni(0) with various phosphines have been investigated by means of DFT calculations. Reasonable linear correlation has been found between Tolman’s electronic parameters (TEPs) and the asymmetric stretching frequency of the coordinated CO2. Two descriptors from EDA-NOCV calculations, namely the interaction energy and the Hirshfeld charge associated with the back donation component gave acceptable linear correlation as well with the TEPs. The coordination strength, as well as the CO bond order in coordinated carbon dioxide can be tuned by varying the substituents on phosphorus: in the presence of electron withdrawing groups the CO bond remains stronger and Ni-C interaction is weaker, moreover, a new Ni-O bond path is formed; whereas for more basic diphosphines the NiC bond order is higher and the coordinated carbon dioxide possess a weaker CO bond.
ISSN:0022-328X
1872-8561
DOI:10.1016/j.jorganchem.2020.121462