Chelate-assisted carbon-halogen bond cleavage by oxidative addition at a W(O) carbonyl-metal complex: Inorganic-organometallic laboratory experiment for advanced undergraduates

1991 ◽  
Vol 68 (9) ◽  
pp. 786 ◽  
Author(s):  
Brett Lucht ◽  
Mitchell J. Poss ◽  
Thomas G. Richmond
Keyword(s):  
Metal Complex ◽  
Laboratory Experiment ◽  
Halogen Bond ◽  
Bond Cleavage ◽  
Oxidative Addition

scholarly journals Competitive Te-Te and C-Te bond cleavage in the oxidative addition of diaryl and dialkyl ditellurides to Pt(0) centers

2017 ◽  
Vol 836-837 ◽  
pp. 17-25 ◽  
Author(s):  
Minna M. Karjalainen ◽  
Torben Wiegand ◽  
J. Mikko Rautiainen ◽  
Andreas Wagner ◽  
Helmar Görls ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Oxidative Addition

scholarly journals Controlling Non-Native B12 Reactivity and Catalysis in the Transcription Factor CarH

2021 ◽  
Author(s):  
Xinhang Yang ◽  
Benjamin H. R. Gerroll ◽  
Yuhua Jiang ◽  
Amardeep Kumar ◽  
Yasmine S. Zubi ◽  
...  
Keyword(s):  
Transcription Factor ◽  
Vitamin B12 ◽  
Transcription Regulation ◽  
Bond Cleavage ◽  
Oxidative Addition ◽  
Mechanistic Studies ◽  
Organic Transformations ◽  
Carbon Bond ◽  
Wide Range ◽  
Hydride Elimination

Vitamin B12 derivatives catalyze a wide range of organic transformations, but B12-dependent enzymes are underutilized in biocatalysis relative to other metalloenzymes. In this study, we engineered a variant of the transcription factor CarH, called CarH*, that catalyzes styrene C-H alkylation with improved yield and selectivity relative to B12 itself. While the native function of CarH involves transcription regulation via AdoCbl Co(III)-carbon bond cleavage and β-hydride elimination to generate 4’,5’-didehydroadenosine, CarH*-catalyzed styrene alkylation proceeds via non-native oxidative addition and olefin addition coupled with a native-like β-hydride elimination. Mechanistic studies on this reaction echo findings from earlier studies on AdoCbl homolysis under strong cage conditions to suggest that CarH* can enable non-native radical chemistry with improved selectivity relative to B12 itself. These findings lay the groundwork for the development of B12-dependent enzymes as catalysts for a wide range of non-native transformations.

scholarly journals Computational study on the mechanism of metal-free photochemical borylation of aryl halides

2021 ◽  
Author(s):  
Chenhao Tu ◽  
Nana Ma ◽  
Qingli Xu ◽  
Wenyue Guo ◽  
Lanxin Zhou ◽  
...  
Keyword(s):  
Density Functional ◽  
Uv Light ◽  
Computational Study ◽  
Halogen Bond ◽  
Bond Cleavage ◽  
Aryl Halides ◽  
Homolytic Cleavage ◽  
Functional Theory ◽  
Aryl Radicals

C-radical borylation is an significant approach for the construction of carbon−boron bond. Photochemical borylation of aryl halides successfully applied this strategy. However, precise mechanisms, such as the generation of aryl radicals and the role of base additive(TMDAM) and water, remain controversy in these reactions. In this study, photochemical borylation of aryl halides has been researched by density functional theory (DFT) calculations. Indeed, the homolytic cleavage of the C−X bond under irradiation with UV-light is a key step for generation of aryl radicals. Nevertheless, the generation of aryl radicals may also undergo the process of single electron transfer and the heterolytic carbon-halogen bond cleavage sequence, and the latter is favorable during the reaction.

Au@Pd Bimetallic Nanocatalyst for Carbon–Halogen Bond Cleavage: An Old Story with New Insight into How the Activity of Pd is Influenced by Au

2018 ◽  
Vol 52 (7) ◽  
pp. 4244-4255 ◽  
Author(s):  
Rui Liu ◽  
Hui-min Chen ◽  
Li-ping Fang ◽  
Cuihong Xu ◽  
Zuoliang He ◽  
...  
Keyword(s):  
Halogen Bond ◽  
Bond Cleavage ◽  
Bimetallic Nanocatalyst ◽  
Insight Into
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