The rhodium benzyl complexes Rh­(diphos*)­(η3-CH2Ph) (1–14, diphos* = chiral bis­(phosphine)), potential precursors for asymmetric catalysis, were prepared either by treatment of Rh­(COD)­(η3-CH2Ph) (15, COD = 1,5-cyclooctadiene) with diphos* or from the reaction of [Rh­(diphos*)­(Cl)]2 (16–20) with PhCH2MgCl, and their structures and dynamics were investigated. For C 2-symmetric diphos* (BPE and DuPhos derivatives, Me-FerroLANE, Et-FerroTANE, DIOP, BINAP), observation of one set of NMR signals for complexes 1–12 suggested that the two diastereomers in which different η3-benzyl enantiofaces were coordinated to rhodium interconverted rapidly on the NMR time scale via suprafacial shifts; observation of five inequivalent aryl 1H NMR signals showed that antarafacial shifts were slow on the NMR time scale. With the C 1-symmetric ligands (R,S)-CyPF-t-Bu and (S,R)-Me-BoPhoz, complexes 13 and 14 gave rise to two sets of NMR signals, consistent with fast suprafacial shifts but slow antarafacial shifts on the NMR time scale. Density functional theory studies of the Me-DuPhos, Me-BPE, Ph-BPE, Me-FerroLANE, and CyPF-t-Bu benzyl complexes 1, 4, 7, 11, and 13 showed that enantioface-selective benzyl coordination involved small energy differences (0.4–2.7 kcal/mol). The barrier to interconversion between these isomers by suprafacial shifts was also low (2.2–7.1 kcal/mol), and the computed barrier for antarafacial shifts in Me-DuPhos complex 1 was significantly higher. Treatment of [Rh­(COD)­(Cl)]2 with PhCH2MgCl gave 15; excess Grignard reagent yielded the ate complex [Mg2Cl3(THF)6]­[Rh­(COD)­(η1-CH2Ph)2] (21). Benzyl complexes 11 and 13, 21, and dimers 17–19 (diphos* = (R,R)-i-Pr-DuPhos, (R,R)-Me-FerroLANE, (R,R)-Ph-BPE) were structurally characterized by X-ray crystallography.

Catalytic asymmetric dehydrocoupling of secondary phosphines is a potentially valuable route to enantiomerically enriched P-stereogenic diphosphines for use as ligands or building blocks for chiral bis(phosphines). Rh(diphos*) catalyst precursors converted a rac/ meso mixture of PhHP(CH 2 ) 3 PHPh (1) to the C 2 -symmetric Pstereogenic anti-diphospholane PhP(CH 2 ) 3 PPh (2) in up to a 58:42 enantiomeric ratio (er) with complete diastereoselectivity via catalystmediated isomerization of the intermediate syn-diphospholane 3 to 2 (mistake correction by conversion of the diastereomer meso-3 to chiral C 2 -2). NMR studies of catalytic reactions identified the resting state Rh((R,R)-i-Pr-DuPhos)(PhHP(CH 2 ) 3 PPh) (4) and suggested a proposed mechanism for stereocontrolled P−P bond formation via oxidative addition and reductive elimination steps.