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 via¹J_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 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.