Abstract
The electronic and steric effects of a series of neutral and ionic (mono-/di-)phosphines on the performance of Ir(I)-complex catalysts for the hydroaminomethylation of olefins were systematically investigated by means of 1J31P-77Se coupling constant measurement, single-crystal X-ray diffraction, and high pressure in situ FTIR spectroscopy. It was found that the neutral mono-phosphines of L1 with the moderate π-accepting nature (1J31P-77Se of 753 Hz) and relatively less steric hindrance was able to spur the activities of the corresponding Ir-catalysts. In addition, the catalytic performances over the Ir(I)- and Rh(I)-precursors was compared under the same reaction conditions. The advantages of Ir(I)-catalyst over Rh(I)-catalyst for this tandem reaction were also discussed in detail.
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