scholarly journals Tactics for probing aryne reactivity: mechanistic studies of silicon–oxygen bond cleavage during the trapping of (HDDA-generated) benzynes by silyl ethers

2014 ◽  
Vol 5 (2) ◽  
pp. 545-550 ◽  
Author(s):  
Thomas R. Hoye ◽  
Beeraiah Baire ◽  
Tao Wang
Keyword(s):  
Bond Cleavage ◽  
Mechanistic Studies ◽  
Silyl Ethers ◽  
Oxygen Bond ◽  
Silicon Oxygen ◽  
Clock Reaction

Mechanistic features of the trapping reaction of an HDDA-generated aryne by pendant silyl ethers were probed using, e.g., an intramolecular clock reaction (cf. k2).

Cofactor characterization and mechanistic studies of CDP-6-deoxy-.DELTA.3,4-glucoseen reductase: Exploration into a novel enzymic carbon-oxygen bond cleavage event

Biochemistry ◽  
1993 ◽  
Vol 32 (44) ◽  
pp. 11934-11942 ◽  
Author(s):  
Vaughn P. Miller ◽  
Jon S. Thorson ◽  
Olivier Ploux ◽  
Stanley F. Lo ◽  
Hung Wen Liu
Keyword(s):  
Bond Cleavage ◽  
Mechanistic Studies ◽  
Oxygen Bond

Photoisomerization of Acylsilanes to Siloxycarbenes, and Their Reactions with Polar Reagents

1973 ◽  
Vol 51 (17) ◽  
pp. 2869-2883 ◽  
Author(s):  
J. M. Duff ◽  
A. G. Brook
Keyword(s):  
Acetic Acid ◽  
Reaction Kinetic ◽  
Bond Cleavage ◽  
Acid Catalyst ◽  
Reaction Pathways ◽  
Acid Catalyzed ◽  
Catalyzed Reactions ◽  
Oxygen Bond ◽  
Silicon Oxygen

The photolysis of acylsilanes in a variety of polar reagents (alcohols, acetic acid, HCN, pyrrole, etc.) is shown to involve formation of isomeric siloxycarbenes which act as nucleophiles and insert into the polar H—X bonds present in the reagents. With alcohols as solvents, mixed acetals of an aldehyde with 1 mol each of silanol and alcohol are formed, but these subsequently undergo dark, acid-catalyzed reactions, by one of two mechanisms which involve either carbon–oxygen or silicon–oxygen bond cleavage. The acid catalyst appears to be a by-product of the photolysis reaction. Kinetic and stereochemical evidence is presented in support of the proposed reaction pathways.

Oxygen-Oxygen Bond Cleavage and Formation in Co(II) Mediated Stoichiometric O2 Reduction via the Potential Intermediacy of a Co(IV) Oxyl Radical

2018 ◽  
Author(s):  
Lucie Nurdin ◽  
Denis M. Spasyuk ◽  
Laura Fairburn ◽  
Warren Piers ◽  
Laurent Maron
Keyword(s):  
Bond Cleavage ◽  
Peroxo Complex ◽  
Oxygen Oxygen ◽  
O2 Reduction ◽  
Oxygen Bond ◽  
Pentadentate Ligand

Diprotonation of a remarkably stable, toluene soluble cobalt peroxo complex supported by a neutral, dianionic pentadentate ligand leads to facile O-O bond cleavage and production of a highly reactive Co(IV) oxyl cation intermediate that dimerizes and releases O<sub>2</sub>. These processes are relevant to both O<sub>2</sub> reduction and O<sub>2</sub> evolution and the mechanism was probed in detail both experimentally and computationally.

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