A series of 2,2′-bis[(dialkylphosphino)methyl]biphenyls (alkyl-BISBIs) were synthesized and applied to the tandem hydroformylation–hydrogenation of 1-decene. The alkyl-BISBI ligands with “small” primary alkyl groups such as methyl or n-hexyl groups on the phosphorus atoms provided 1-alkanols selectively, whereas those with larger alkyl groups such as isopropyl or neopentyl groups showed much lower conversion from alkanals to alkanols. Observation of rhodium complexes of the BISBI-type ligands under H2/CO atmosphere revealed that the presence of a stable [RhH(CO)2(ligand)] species seems to be less favorable for the second step, the hydrogenation of aldehydes.
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