Fluoride anion complexation and transport using a stibonium cation stabilized by an intramolecular P=O→Sb pnictogen bond

2021 ◽  
Author(s):  
Vanessa M. Gonzalez ◽  
Gyeongjin Park ◽  
Mengxi Yang ◽  
François P. Gabbaï
Keyword(s):  
Lewis Acid ◽  
Fluoride Anion ◽  
Anion Complexation

We describe the synthesis of [o-Ph2P(=O)(C6H4)SbPh3]+ ([2]+), an intramolecularly base-stabilized stibonium Lewis acid which was obtained by reaction of [o-Ph2P(C6H4)SbPh3]+ with NOBF4. This cation reacts with fluoride anions to afford...

scholarly journals Unique fluoride anion complexation in basic media by 5,5-dioxophenothiazine bis(phenylurea) and bis(phenylthiourea)

Tetrahedron ◽  
2013 ◽  
Vol 69 (38) ◽  
pp. 8142-8146 ◽  
Author(s):  
Attila Kormos ◽  
Ildikó Móczár ◽  
Dávid Pál ◽  
Péter Baranyai ◽  
Tamás Holczbauer ◽  
...  
Keyword(s):  
Fluoride Anion ◽  
Anion Complexation

Cyanide and Azide Anion Complexation by a Bidentate Stibonium-Borane Lewis Acid

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1199-1205 ◽  
Author(s):  
Casey R. Wade ◽  
François P. Gabbaï
Keyword(s):  
Lewis Acid ◽  
Lewis Acids ◽  
Natural Bond Orbital ◽  
Orbital Method ◽  
Computational Studies ◽  
Cyanide Complex ◽  
Acid Anion ◽  
Anion Complexation ◽  
Azide Ligand ◽  
Complex Features

Abstract Our ongoing interest in the chemistry of polyfunctional Lewis acids has led us to investigate the reaction of the stibonium-borane [o-(Ph2MeSb)(Mes2B)C6H4]+ (1+) with cyanide and azide, two toxic anions. Both anions react with 1+ to afford the corresponding neutral complexes 1-CN and 1-N3. Structural and computational studies show that the coordinated anion interacts with both the boron and antimony atoms of the bidentate Lewis acid. While the azide complex features a typical κ2N1 : N1 bridging azide ligand, the cyanide complex possesses a cyanoborate moiety whose cyanide interacts side-on with the stibonium center. The Lewis acid-anion interactions observed in these complexes have also been studied computationally using the Natural Bond Orbital method

Fluoride Anion Chelation by a Bidentate Stibonium–Borane Lewis Acid

2011 ◽  
Vol 30 (17) ◽  
pp. 4479-4481 ◽  
Author(s):  
Casey R. Wade ◽  
François P. Gabbaï
Keyword(s):  
Lewis Acid ◽  
Fluoride Anion

CHEMICAL EFFECTS IN MULTIELECTRON PROCESSES IN THE FLUORIDE ANION

1987 ◽  
Vol 48 (C9) ◽  
pp. C9-777-C9-780
Author(s):  
R. HESSABI ◽  
D. URCH
Keyword(s):  
Fluoride Anion ◽  
Chemical Effects

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.

Catalytic Carbonyl-Olefin Metathesis of Aliphatic Ketones: Iron(III) HomoDimers as Lewis Acidic Superelectrophiles

2018 ◽  
Author(s):  
Haley Albright ◽  
Paul S. Riehl ◽  
Christopher C. McAtee ◽  
Jolene P. Reid ◽  
Jacob R. Ludwig ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Olefin Metathesis ◽  
Acid Activation ◽  
Lewis Acid Catalysts ◽  
Distinct Mode ◽  
Aliphatic Ketones ◽  
Carbon Carbon Bond ◽  
Metathesis Reactions ◽  
Acid Catalyzed

<div>Catalytic carbonyl-olefin metathesis reactions have recently been developed as a powerful tool for carbon-carbon bond</div><div>formation. However, currently available synthetic protocols rely exclusively on aryl ketone substrates while the corresponding aliphatic analogs remain elusive. We herein report the development of Lewis acid-catalyzed carbonyl-olefin ring-closing metathesis reactions for aliphatic ketones. Mechanistic investigations are consistent with a distinct mode of activation relying on the in situ formation of a homobimetallic singly-bridged iron(III)-dimer as the active catalytic species. These “superelectrophiles” function as more powerful Lewis acid catalysts that form upon association of individual iron(III)-monomers. While this mode of Lewis acid activation has previously been postulated to exist, it has not yet been applied in a catalytic setting. The insights presented are expected to enable further advancement in Lewis acid catalysis by building upon the activation principle of “superelectrophiles” and broaden the current scope of catalytic carbonyl-olefin metathesis reactions.</div>

Sign in / Sign up

Export Citation Format

Share Document