Synthesis and use of borane and platinum(II) complexes of 3‐diphenylphosphino‐1‐ phenylphospholane (LuPhos)

3‐Diphenylphosphinoyl‐1‐phenylphospholane 1‐oxide ( 2 ) obtained by the Michael addition of diphenylphosphine oxide to the double‐bond of 1‐phenyl‐2‐phospholene 1‐oxide ( 1 ) was subjected to double deoxygenation to afford the corresponding bisphosphine ( 3 , LuPhos) that was converted to bis(phosphine borane) 4 and to cis chelate platinum(II) complex 6 . A mixed phosphine oxide–phosphine borane 5 was also prepared. Stereostructures of the bidentate P‐ligand 3 and the ring platinum(II) complex ( 6 ) were evaluated by quantum chemical calculations. Complex 6 used as a catalyst showed modest activity, but unusual regioselectivity in the hydroformylation of styrene and its 4‐substituted analogues. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:730–736, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20741