1287211-69-1Relevant academic research and scientific papers
Rhodium(I)-Catalyzed Tertiary Phosphine Directed C?H Arylation: Rapid Construction of Ligand Libraries
Qiu, Xiaodong,Wang, Minyan,Zhao, Yue,Shi, Zhuangzhi
, p. 7233 - 7237 (2017)
Modification of commercially available monophosphine ligands with either aryl bromides or chlorides by rhodium(I)-catalyzed, tertiary phosphine directed C?H activation is described. A series of ligand libraries containing mono- and diaryl-substituted groups, having different steric and electronic properties, were obtained in high yields. Based on the outstanding properties of their parent scaffolds, the modified ligands have been found to be powerful in organic reactions.
Synthesis, characterization, and reactivity of arene-stabilized rhodium complexes
O'Connor, Abby R.,Kaminsky, Werner,Heinekey, D. Michael,Goldberg, Karen I.
, p. 2105 - 2116 (2011/06/22)
The synthesis and characterization of (COD)Rh(I) and (NBD)Rh(I) (COD = cyclooctadiene; NBD = norbornadiene) chloride complexes containing the 2-(dicyclohexylphosphino)biphenyl (PCy2biPh) ligand are reported. Abstraction of the halide with Na(BArF)4 yields cationic Rh(I) complexes [(NBD)Rh(PCy2biPh)][B(ArF)4] (2) and [(COD)Rh(PCy2biPh)][B(ArF)4] (7) (ArF = 3,5-bis(trifluoromethyl)phenyl). In complex 2, the pendent arene of the ligand is coordinated in an η2-fashion to rhodium. Complex 7 exists in two configurations that were characterized by low-temperature NMR spectroscopy. One structure is analogous to 2 with η2-coordination of the arene, and the other exhibits η6-coordination. These structures interconvert on the NMR time scale at room temperature. Addition of H2 to complex 2 yields the Rh(III) dihydride complex [(PCy2biPh)RhH2][B(Ar F)4] (5), while the addition of H2 to 7 generates the Rh(I) olefin complex [(COE)Rh(PCy2biPh)][B(Ar F)4] (8). In both 5 and 8, the pendent arene of the ligand is bound η6 to Rh. Benzene hydrogenation to cyclohexane using 2 as a catalyst precursor is described. Poisoning experiments indicate that heterogeneous rhodium is likely to be the active catalyst in this arene hydrogenation reaction.
