Bulky 1, 1′-bisphosphanoferrocenes and their coordination behaviour towards Cu(i). Issue 20 (28th April 2020)

• Record Type: Journal Article
• Authors: Dey, Subhayan; Buzsáki, Daniel; Bruhn, Clemens; Kelemen, Zsolt; Pietschnig, Rudolf
• Is Part Of: Dalton transactions. Volume 49:Issue 20(2020)
• Page Start: 6668
• Page End: 6681
• Publication Date: 2020-04-28
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d0dt00941e
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Bulky dppf analogues have been reported for which donor properties and coordination behavior have been explored and tested in a catalytic model reaction. Abstract : Two bulky mesityl substituted dppf-analogues Fe(C5 H4 PMes2 )2 (Mes = 2, 4, 6-Me3 C6 H2, 1 ) and Fe(C5 H4 PMes2 )(C5 H4 PPh2 ) (Mes = 2, 4, 6-Me3 C6 H2, Ph = C6 H5, 3 ) have been prepared and their properties as donor ligands have been explored using heteronuclear NMR spectroscopy and in particular via 1 J P–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 Cu2 Br2 units, while for the other dinuclear complexes planar Cu2 Br2 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.