Iron carbonyl complex containing bis[2‐(diphenylphosphino)phenyl]ether enhancing efficiency in the palladium‐catalyzed Suzuki–Miyaura reaction

The reaction of [Fe 3 (CO) 12 ] with bis[2‐(diphenylphosphino)phenyl]ether (DPEphos) in refluxing THF afforded a mononuclear complex, [Fe(CO) 4 (η 1 ‐P‐DPEphos)] (1), as major product and a binuclear complex, [Fe 2 (CO) 6 (μ‐CO)(μ‐P,P‐DPEphos)] (2), as minor product respectively. The DPEphos ligand acts as a terminal P‐donor in complex 1 and a bridging P,P‐donor in complex 2. Complexes 1 and 2 were characterized by elemental analysis, fast atom bombardment mass spectrometry, FT‐IR, 1 H and 31 P{ 1 H} NMR spectroscopy. The structure of complex 1 has been tentatively assigned by density functional theory calculations and its analogy with reported complexes. Combination of complex 1 and PdCl 2 furnished an active catalyst for the Suzuki–Miyaura cross‐coupling reactions of various aryl halides with arylboronic acids. Interestingly, under the same experimental condition, complex 1/PdCl 2 as catalyst showed superior activity over the DPEphos/PdCl 2 system. Copyright © 2012 John Wiley & Sons, Ltd.