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• W3093043994 endingPage "3816" @default.
• W3093043994 startingPage "3802" @default.
• W3093043994 abstract "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 1–12 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 C1-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." @default.
• W3093043994 created "2020-10-22" @default.
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• W3093043994 date "2020-10-16" @default.
• W3093043994 modified "2023-09-25" @default.
• W3093043994 title "Synthesis, Structure, Dynamics, and Enantioface-Selective η³-Benzyl Coordination in the Chiral Rhodium Complexes Rh(diphos*)(η³-CH₂Ph)" @default.
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• W3093043994 doi "https://doi.org/10.1021/acs.organomet.0c00516" @default.
• W3093043994 hasPublicationYear "2020" @default.
• W3093043994 type Work @default.
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