112270-12-9Relevant academic research and scientific papers
Triplet Ground-State Benzoylphenylmethylene and Its Quintet Ground-State Triplet-Triplet Radical Pair
Murai, H.,Safarik, I.,Torres, M.,Strausz, O. P.
, p. 1025 - 1032 (1988)
Photolysis of crystalline azibenzil powder at 77 K and λ >/= 345 nm generates a complex ESR spectrum consisting of four components, namely a strong triplet, a weak triplet, a quintet, and a doublet.The strong triplet has been previously assigned to ground-state benzoylphenylmethylene and the quintet to the ground state of a radical pair formed between two triplet benzoylphenylmethylenes.On the basis of the similar values exhibited by the zero-field splitting parameters, the strong and weak triplet signals are assigned here to the s-Z and s-E isomers of the ground state of benzoylphenylmethylene, respectively.The s-Z conformer is more abundant and less stable than the s-E, and on annealing, the decay of both signals follows first-order kinetics.Above 90 K the quintet radical pair also decays with first-order kinetics to yield a new triplet diradical, which is stable at T 120 K but disappears with first-order kinetics above 120 K.The Arrhenius parameters have been determined for all decay reactions and utilized in their mechanistic interpretation.The carrier of the structureless, broad doublet signal observed appears to be generated from the secondary photolysis of the tiplet benzoylphenylmethylene.The assignment of the quintet spectrum to a radical pair is also supported by the absence of this spectrum in the photolysate of dilute azibenzil solutions in glassy matrices.Under such conditions, in addition to the spectrum of benzoylphenylmethylene and its doublet photolysis products, a new triplet diradical appears wiht a kinetics of formation suggesting that it is formed by the decay of the quintet.However, its identity has not been established.
Gold-Catalyzed Oxidative [2+2+1] Annulations of Aryldiazo Nitriles with Imines To Yield Polyarylated Imidazolium Salts
Pawar, Samir Kundlik,Yang, Ming-Chung,Su, Ming-Der,Liu, Rai-Shung
, p. 5035 - 5039 (2017)
Gold-catalyzed oxidative [2+2+1] annulations between two imines and one α-cyano arylgold carbene afforded polyarylated imidazolium salts and molecular hydrogen efficiently. Control experiments suggest that the gold catalyst alone facilitates the main annulation, whereas Ag+ avoids the formation of inactive LAuCN. DFT calculations suggest that the success of this annulation relies on a 6 π-electrocyclization of cyano-free intermediates with cis-configured imines as initial reagents.
Reactivity of Lutetacyclopropene toward Benzyl, Benzoyl, and Trimethylsilyl Nitriles Affording Diversified Lutetium Complexes
Lv, Ze-Jie,Zhu, Miaomiao,Liu, Wei,Chai, Zhengqi,Wei, Junnian,Zhang, Wen-Xiong
supporting information, p. 3992 - 3998 (2021/12/02)
Although the reaction of metallacyclopropenes toward alkyl and aryl nitriles has been extensively studied, their reactivity toward other types of nitriles, e.g., benzyl and benzoyl nitriles, that often behave multifunctionally was rarely explored. Herein,
Cyanine-based near infra-red organic photoredox catalysis
Baralle, Alexandre,Cormier, Morgan,Goddard, Jean-Philippe,Obah Kosso, Anne Roly,Sellet, Nicolas
, p. 6964 - 6968 (2021/06/02)
Direct metal-free near infra-red photoredox catalysis is applied to organic oxidation, photosensitization and reduction, involving cyanines as photocatalysts. This photocatalyst is competitive with conventional reactions catalyzed under visible light. Kin
Reactions of Diphenylcyclopropenone and Tetracyclones with Potassium Superoxide
Neckers, Douglas C.,Hauck, Gerhard
, p. 4691 - 4695 (2007/10/02)
Reactions of diphenylcyclopropenone and various tetracyclones with potassium superoxide are reported.
Reactions of low-valent titanium with various functional groups (phenyl derivatives)
Dams, Rudy,Malinowski, Marek,Giese, Herman J.
, p. 112 - 114 (2007/10/02)
Titanium slurries, prepared by reduction of titanium chlorides with LiAlH4, are not only effective in couplings of ketones and aldehydes to alkenes, but also in reductive couplings and reductions of other functional groups.
Mechanism of Thermolysis of Endoperoxides of Aromatic Compounds. Activation Parameters, Magnetic Field, and Magnetic Isotope Effecs
Turro, Nicholas J.,Chow, Ming-Fea,Rigaudy, Jean
, p. 7218 - 7224 (2007/10/02)
A mechanistic investigation has been made of the thermolysis of several endoperoxides of anthracenes and naphthalenes which produce molecular oxygen and the parent aromatic species quantitatively.Qualitative thermochemical measurements in the solid state indicate that in all cases studied, the reactions were endothermic.This situation appears to be valid in solution also.Clean first-order kinetics were observed for these thermolyses.Activation parameters were derived from the temparature dependence of the first-order rate constants.The primary yields of singlet oxygen (1O2) from the several endoperoxides were determined, and a correlation was discovered between the A factors (ΔS values) for thermolysis and the yield of 1O2.It was found that high A factors (positive ΔS values) correlated with relatively low yields of 1O2 and that low A factors (slightly negative or near zero ΔS values) correlated with nearly quantitative yields of 1O2.These two results are interpreted in terms of a diradical mechanism which leads to low yield of 1O2 and a concerted mechanism which leads to quantitative yields of 1O2.This interpretation is consistent with the observation of a magnetic field effect on the yield of 1O2 from endoperoxides whose thermolyses proceed with positive ΔS values and the absence of a magnetic field effect on the yield of 1Oi endoperoxides whose thermolyses proceed with near zero ΔS values.Further support for the occurrence of a diradical mechanism is available from the demonstration of a special 17O isotope effect on the thermolysis of an endoperoxide which is postulated to undergo thermolysis principally via a diradical intermediate.The thermolysis of endoperoxides which decompose mainly by a diradical mechanism yields triplet molecular oxygen that is selectively enriched in 17O.
