13406-27-4Relevant articles and documents
Chemistry of singlet oxygen with arylphosphines
Zhang, Dong,Ye, Bin,Ho, David G.,Gao, Ruomei,Selke, Matthias
, p. 10729 - 10733 (2006)
The chemistry of singlet oxygen with a variety of arylphosphines has been studied. Rates of singlet oxygen removal by para-substituted arylphosphines show good correlation with the Hammett σ parameter (ρ=-1.53 in CDCl3), and with the Tolman electronic parameter. The only products for the reactions of these phosphines with singlet oxygen are the corresponding phosphine oxides. Conversely, for ortho-substituted phosphines with electron-donating substituents, there are two products, namely a phosphinate formed by intramolecular insertion and phosphine oxide. Kinetic analyses demonstrate that both products are formed from the same intermediate, and this allows determination of the rate ratios for the competing pathways. Increasing the steric bulk of the phosphine leads to an increase in the amount of insertion product. VT NMR experiments show that peroxidic intermediates can only be detected for very hindered and very electron-rich arylphosphines.
THE SYNTHESIS OF TRIS-(TRIFLUOROMETHYLPHENYL)PHOSPHINES AND PHOSPHINE OXIDES
Eapen, Kalathil C.,Tamborski, Christ
, p. 239 - 244 (1980)
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Mechanism of O-Atom Transfer from Nitrite: Nitric Oxide Release at Copper(II)
Stauffer, Molly,Sakhaei, Zeinab,Greene, Christine,Ghosh, Pokhraj,Bertke, Jeffery A.,Warren, Timothy H.
supporting information, p. 15968 - 15974 (2021/07/26)
Nitric oxide (NO) is a key signaling molecule in health and disease. While nitrite acts as a reservoir of NO activity, mechanisms for NO release require further understanding. A series of electronically varied β-diketiminatocopper(II) nitrite complexes [CuII](κ2-O2N) react with a range of electronically tuned triarylphosphines PArZ3 that release NO with the formation of O═PArZ3. Second-order rate constants are largest for electron-poor copper(II) nitrite and electron-rich phosphine pairs. Computational analysis reveals a transition-state structure energetically matched with experimentally determined activation barriers. The production of NO follows a pathway that involves nitrite isomerization at CuII from κ2-O2N to κ1-NO2 followed by O-atom transfer (OAT) to form O═PArZ3 and [CuI]-NO that releases NO upon PArZ3 binding at CuI to form [CuI]-PArZ3. These findings illustrate important mechanistic considerations involved in NO formation from nitrite via OAT.
Ir(III)-catalyzed direct C-H functionalization of arylphosphine oxides: A strategy for MOP-type ligands synthesis
Liu, Zhong,Wu, Ji-Qiang,Yang, Shang-Dong
supporting information, p. 5434 - 5437 (2017/11/06)
Diazo compounds as coupling partners are efficiently applied to Ir(III)-catalyzed direct C-H functionalization of arylphos-phine oxides. Involving C-H activation, carbene insertion, and tautomerism, this reaction proceeds under mild conditions, thus proving an approach to the synthesis of MOP-type ligand precursor in a single step. The utility of this transformation has been further demonstrated in ligand synthesis as well as in the construction of phosphole framework.