New diphosphines based on benzofurobenzofuran and dibenzodioxocin backbones, forming exclusively bimetallic complexes were designed and synthesized. Depending on the ligand to metal ratio, face-to-face bimetallic complexes or syn-chloride bridged dimeric complexes were formed as main reaction products. The structures of the rhodium complexes of the new ligands 4, 7, 10, 13, 16 were established in solution by NMR, IR, and MS spectroscopy. The molecular structures of the syn-chloride bridged dimeric complexes [Rh2(CO)2(μ-Cl)2(4)] (22), [Rh2(CO)2(μ-Cl)2(10)] (24), and the face-to-face bimetallic complexes [Rh(CO)Cl(4)]2 (17), [Rh(CO)Cl(10)]2 (19), and [Rh(CO)Cl(13)]2 (20) were confirmed by X-ray crystallography. Ligands 4, 7, 10, 13, 16, and SPANphos were tested in rhodium catalyzed methanol carbonylation at 150 °C and 22 bar of CO gas, showing high activities under catalytic conditions.
