Issue 20, 2020

Bulky 1,1′-bisphosphanoferrocenes and their coordination behaviour towards Cu(i)


Two bulky mesityl substituted dppf-analogues Fe(C5H4PMes2)2 (Mes = 2,4,6-Me3C6H2, 1) and Fe(C5H4PMes2)(C5H4PPh2) (Mes = 2,4,6-Me3C6H2, Ph = C6H5, 3) have been prepared and their properties as donor ligands have been explored using heteronuclear NMR spectroscopy and in particular via1JP–Se coupling, cyclic voltammetry and DFT calculations. Based on the results obtained, a series of mono- and dinuclear Cu(I) complexes have been prepared with these new diphosphane ligands using Br, I, and BF4 as counter anions. For the very bulky ligand 1 rare and unprecedented double bridging complexation modes have been observed containing two non-planar Cu2Br2 units, while for the other dinuclear complexes planar Cu2Br2 units have been found. The Cu(I) complexes of 1 and 3 were then used as catalysts for CO2-fixation reaction with terminal alkynes, and complexes with ligand 3 were found to be more efficient than those with 1. DFT calculations performed on compounds 1, 3 and their Cu(I) complexes were able to verify the trend of these catalytic reactions.

Graphical abstract: Bulky 1,1′-bisphosphanoferrocenes and their coordination behaviour towards Cu(i)

Supplementary files

Article information

Article type
12 Mar 2020
07 Apr 2020
First published
08 Apr 2020
This article is Open Access
Creative Commons BY license

Dalton Trans., 2020,49, 6668-6681

Bulky 1,1′-bisphosphanoferrocenes and their coordination behaviour towards Cu(I)

S. Dey, D. Buzsáki, C. Bruhn, Z. Kelemen and R. Pietschnig, Dalton Trans., 2020, 49, 6668 DOI: 10.1039/D0DT00941E

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