Valence Tautomerism in a High-Valent Manganese–Oxo Porphyrinoid Complex Induced by a Lewis Acid

2012 ◽  
Vol 134 (25) ◽  
pp. 10397-10400 ◽  
Author(s):  
Pannee Leeladee ◽  
Regina A. Baglia ◽  
Katharine A. Prokop ◽  
Reza Latifi ◽  
Sam P. de Visser ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Valence Tautomerism ◽  
High Valent

How does Lewis acid affect the reactivity of mononuclear high‐valent chromium–oxo species? A theoretical study

2021 ◽  
Author(s):  
Yunhee Choi ◽  
Bhawana Pandey ◽  
Xiao‐Xi Li ◽  
Yong‐Min Lee ◽  
Kyung‐Bin Cho ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Theoretical Study ◽  
High Valent

scholarly journals Activation of a High-Valent Manganese–Oxo Complex by a Nonmetallic Lewis Acid

2014 ◽  
Vol 53 (12) ◽  
pp. 5893-5895 ◽  
Author(s):  
Regina A. Baglia ◽  
Maximilian Dürr ◽  
Ivana Ivanović-Burmazović ◽  
David P. Goldberg
Keyword(s):  
Lewis Acid ◽  
High Valent

scholarly journals Tuning the Geometric and Electronic Structure of Synthetic High-Valent Heme Iron(IV)-Oxo Models in the Presence of a Lewis Acid and Various Axial Ligands

2019 ◽  
Vol 141 (14) ◽  
pp. 5942-5960 ◽  
Author(s):  
Melanie A. Ehudin ◽  
Leland B. Gee ◽  
Sinan Sabuncu ◽  
Augustin Braun ◽  
Pierre Moënne-Loccoz ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Lewis Acid ◽  
Heme Iron ◽  
Axial Ligands ◽  
High Valent

Valence-tautomerism in high-valent iron and manganese porphyrins

2001 ◽  
Vol 6 (8) ◽  
pp. 831-845 ◽  
Author(s):  
Raymond Weiss ◽  
Véronique Bulach ◽  
Avram Gold ◽  
James Terner ◽  
Alfred X. Trautwein
Keyword(s):  
Valence Tautomerism ◽  
Manganese Porphyrins ◽  
High Valent ◽  
Iron And Manganese

Toward a Comprehensive Treatment of Tautomerism in Chemoinformatics Including in InChI V2

2019 ◽  
Author(s):  
Devendra K. Dhaked ◽  
Wolf Ihlenfeldt ◽  
Hitesh Patel ◽  
Marc Nicklaus
Keyword(s):  
Small Molecule ◽  
Comprehensive Treatment ◽  
Experimental Literature ◽  
Web Tool ◽  
Valence Tautomerism ◽  
Standard Version ◽  
Small Molecule Databases

<p>We have collected 86 different transforms of tautomeric interconversions. Out of those, 54 are for prototropic (non-ring-chain) tautomerism; 21 for ring-chain tautomerism; and 11 for valence tautomerism. The majority of these rules have been extracted from experimental literature. Twenty rules – covering the most well-known types of tautomerism such as keto-enol tautomerism – were taken from the default handling of tautomerism by the chemoinformatics toolkit CACTVS. The rules were analyzed against nine differerent databases totaling over 400 million (non-unique) structures as to their occurrence rates, mutual overlap in coverage, and recapitulation of the rules’ enumerated tautomer sets by InChI V.1.05, both in InChI’s Standard and a Non-Standard version with the increased tautomer-handling options 15T and KET turned on. These results and the background of this study are discussed in the context of the IUPAC InChI Project tasked with the redesign of handling of tautomerism for an InChI version 2. Applying the rules presented in this paper would approximately triple the number of compounds in typical small-molecule databases that would be affected by tautomeric interconversion by InChI V2. A web tool has been created to test these rules at https://cactus.nci.nih.gov/tautomerizer.</p>

Cobalt/Lewis Acid Catalysis for Hydrocarbofunctionalization of Alkynes via Cooperative C–H Activation

2020 ◽  
Author(s):  
Chang-Sheng Wang ◽  
Sabrina Monaco ◽  
Anh Ngoc Thai ◽  
Md. Shafiqur Rahman ◽  
Chen Wang ◽  
...  
Keyword(s):  
Catalytic System ◽  
Lewis Acid ◽  
Hydrogen Transfer ◽  
Acid Catalysis ◽  
Rate Limiting Step ◽  
Site Selectivity ◽  
Set Up ◽  
Site Selective ◽  
First Time ◽  
Rate Limiting

A catalytic system comprised of a cobalt-diphosphine complex and a Lewis acid (LA) such as AlMe3 has been found to promote hydrocarbofunctionalization reactions of alkynes with Lewis basic and electron-deficient substrates such as formamides, pyridones, pyridines, and azole derivatives through site-selective C-H activation. Compared with known Ni/LA catalytic system for analogous transformations, the present catalytic system not only feature convenient set up using inexpensive and bench-stable precatalyst and ligand such as Co(acac)3 and 1,3-bis(diphenylphosphino)propane (dppp), but also display distinct site-selectivity toward C-H activation of pyridone and pyridine derivatives. In particular, a completely C4-selective alkenylation of pyridine has been achieved for the first time. Mechanistic stidies including DFT calculations on the Co/Al-catalyzed addition of formamide to alkyne have suggested that the reaction involves cleavage of the carbamoyl C-H bond as the rate-limiting step, which proceeds through a ligand-to-ligand hydrogen transfer (LLHT) mechanism leading to an alkyl(carbamoyl)cobalt intermediate.

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