63589-56-0Relevant articles and documents
Synthesis, Reactivity, and Coordination of Semihomologous dppf Congeners Bearing Primary Phosphine and Primary Phosphine Oxide Groups
Horky, Filip,Císa?ová, Ivana,?těpni?ka, Petr
, p. 427 - 441 (2021/02/06)
This contribution reports the synthesis of two phosphinoferrocene ligands desymmetrized by an inserted methylene spacer, viz., a bis-phosphine combining primary and tertiary phosphine moieties in its structure, Ph2PfcCH2PH2 (2), and a structurally unique, stable phosphine-primary phosphine oxide Ph2PfcCH2P(O)H2 (7; fc = ferrocene-1,1′-diyl). Compounds 2 and 7, together with 1,1′-bis(diphenylphosphino)ferrocene (dppf), the bis-tertiary phosphine Ph2PfcCH2PPh2, and the adduct Ph2P(BH3)fcCH2PH2 (6), were studied as ligands in Ru(II) complexes bearing auxiliary ν6-arene ligands and both free ligands and the isolated complexes were structurally authenticated, using spectroscopic methods and X-ray crystallography, and further investigated by cyclic voltammetry. The results suggest that distinct donor moieties in the unsymmetric ligands differentiate the otherwise identical coordinated metal centers and that the phosphine moiety in phosphine-phosphine oxide ligand 7 is preferably coordinated to Ru(II), before the phosphine oxide group, which must tautomerize into the hydroxyphosphine form prior to coordination.
Iron Catalyzed Double Bond Isomerization: Evidence for an FeI/FeIII Catalytic Cycle
Woof, Callum R.,Durand, Derek J.,Fey, Natalie,Richards, Emma,Webster, Ruth L.
supporting information, p. 5972 - 5977 (2021/03/17)
Iron-catalyzed isomerization of alkenes is reported using an iron(II) β-diketiminate pre-catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H3N?BH3). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre-catalyst activation step that gives access to an η2-coordinated alkene FeI complex, followed by oxidative addition of the alkene to give an FeIII intermediate, which then undergoes reductive elimination to allow release of the isomerization product.
PET-RAFT single unit monomer insertion of β-methylstyrene derivatives: RAFT degradation and reaction selectivity
Lin, Shiyang,Liu, Ruizhe,Xu, Jiangtao,Zhang, Lei
supporting information, p. 10759 - 10762 (2021/10/20)
Reversible addition-fragmentation chain transfer (RAFT) single unit monomer insertion (SUMI) of β-methylstyrene derivatives into diverse RAFT agents presented fast reaction kinetics, but significant degradation of the SUMI products occurred due to a hydrogen abstraction reaction. Fortunately, such degradation can be suppressed through appropriate design of initial RAFT agents attributed to effective chain transfer and selective photoactivation.
