| Abstrakt: |
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 C2-symmetric diphos* (BPE and DuPhos derivatives, Me-FerroLANE, Et-FerroTANE, DIOP, BINAP), observation of one set of NMR signals for complexes 1–12suggested 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 C1-symmetric ligands (R,S)-CyPF-t-Bu and (S,R)-Me-BoPhoz, complexes 13and 14gave 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 13showed 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 1was significantly higher. Treatment of [Rh(COD)(Cl)]2with PhCH2MgCl gave 15; excess Grignard reagent yielded the ate complex [Mg2Cl3(THF)6][Rh(COD)(η1-CH2Ph)2] (21). Benzyl complexes 11and 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. |
