Electric Literature of 6224-63-1, As an important bridge between the micro and macro material world, chemistry is one of the main methods and means for humans to understand and transform the material world. 6224-63-1, Name is Tri-m-tolylphosphine, SMILES is CC1=CC(P(C2=CC=CC(C)=C2)C3=CC=CC(C)=C3)=CC=C1, belongs to chiral-phosphine-ligands compound. In a article, author is Scheetz, Perry M., introduce new discover of the category.
Synthesis, Structure, Dynamics, and Enantioface-Selective eta(3)-Benzyl Coordination in the Chiral Rhodium Complexes Rh(diphos*)(eta(3)-CH2Ph)
The rhodium benzyl complexes Rh(diphos*)(eta(3)-CH2Ph) (1-14, diphos* = chiral bis(phosphine)), potential precursors for asymmetric catalysis, were prepared either by treatment of Rh(COD)(eta(3)-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 eta(3)-benzyl enantiofaces were coordinated to rhodium interconverted rapidly on the NMR time scale via suprafacial shifts; observation of five inequivalent aryl H-1 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)(eta(1)-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.
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Reference:
Phosphine ligand,
,Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate