Decarboxylation to Unmask Organometallics: Scope and Utility in Bond Formation

Bringing a Mechanistic Lens to the Development of New Transfer Hydroarylation Isodesmic Reactions for the Synthesis of Amides, Thioamides, Amidines, Alkenes and Ketones from Carboxylic Acids via Extrusion and Insertion Elementary Steps

RAJ O'Hair

2023-08-01

The wide availability, ease of handling and structural and functional diversity make carboxylic acids prized building blocks in or..

ORGANOMETALLIC GAS-PHASE ION CHEMISTRY AND CATALYSIS: INSIGHTS INTO THE USE OF METAL CATALYSTS TO PROMOTE SELECTIVITY IN THE REACTIONS OF CARBOXYLIC ACIDS AND THEIR DERIVATIVES

RAJ O'Hair

2021-11-01

Carboxylic acids are valuable organic substrates as they are widely available, easy to handle, and exhibit structural and function..

Gas-Phase and Computational Study of Identical Nickel- and Palladium-Mediated Organic Transformations Where Mechanisms Proceeding via MII or MIV Oxidation States Are Determined by Ancillary Ligands

KL Vikse, GN Khairallah, A Ariafard, AJ Canty, RAJ OHair

2015-10-28

Gas-phase studies utilizing ion-molecule reactions, supported by computational chemistry, demonstrate that the reaction of the eno..

Prying open a Reactive Site for Allylic Arylation by Phosphine-Ligated Geminally Diaurated Aryl Complexes

KL Vikse, A Zavras, TH Thomas, A Ariafard, GN Khairallah, AJ Canty, BF Yates, RAJ O'Hair

2015-07-13

Gas-phase ion-molecule reaction experiments, theoretical kinetic modeling, and computational chemistry were used to examine the ro..

Copper mediated decyano decarboxylative coupling of cyanoacetate ligands: Pesci versus Lewis acid mechanism

J Li, GN Khairallah, V Steinmetz, P Maitre, RAJ O'Hair

2015-05-21

A combination of gas-phase ion trap multistage mass spectrometry (MSⁿ) experiments and density functional theory (DFT) ..

Gas-phase studies of metal catalyzed decarboxylative cross-coupling reactions of esters

RAJ O'Hair

2015-04-01

Metal-catalyzed decarboxylative coupling reactions of esters offer new opportunities for formation of C-C bonds with CO<inf>2</inf..

Gas phase studies of the Pesci decarboxylation reaction: Synthesis, structure, and unimolecular and bimolecular reactivity of organometallic ions

RAJ O'Hair, NJ Rijs

2015-02-17

ConspectusDecarboxylation chemistry has a rich history, and in more recent times, it has been recruited in the quest to develop ch..

Dimethylcuprate-mediated transformation of acetate to dithioacetate

J Li, GN Khairallah, RAJ O'Hair

2015-01-26

Dithiocarboxylic acids, RCS<inf>2</inf>H, and their esters, RCS<inf>2</inf>R′, are useful reagents that can be synthesized by the ..

Decarboxylation versus Acetonitrile Loss in Silver Acetate and Silver Propiolate Complexes, [RCO2Ag2(CH3CN)n] (where R = CH3 and CH3C≡C; N = 1 and 2)

J Li, GN Khairallah, RAJ O'Hair

2015-01-01

Gas-phase experiments using collision-induced dissociation in an ion trap mass spectrometer have been used in combination with den..

Decarboxylative-coupling of allyl acetate catalyzed by group 10 organometallics, [(phen)M(CH3)]

M Woolley, A Ariafard, GN Khairallah, KH Kwan, PS Donnelly, JM White, AJ Canty, BF Yates, RAJ O'Hair

2014-12-19

Gas-phase carbon-carbon bond forming reactions, catalyzed by group 10 metal acetate cations [(phen)M(O<inf>2</inf>CCH<inf>3</inf>)..

Direct versus water-mediated protodecarboxylation of acetic acid catalyzed by group 10 carboxylates, [(phen)M(O2CCH3)]

M Woolley, GN Khairallah, G Da Silva, PS Donnelly, RAJ Ohair

2014-10-13

The gas-phase protodecarboxylation of acetic acid catalyzed by group 10 metal complexes was examined using a combination of multis..

Molecular Salt Effects in the Gas Phase: Tuning the Kinetic Basicity of [HCCLiCl]⁻ and [HCCMgCl₂]⁻ by LiCl and MgCl₂

George N Khairallah, Gabriel da Silva, Richard AJ O'Hair

2014-10-06

<jats:title>Abstract</jats:title><jats:p>A combination of gas‐phase ion–molecule reaction experiments and theoretical kinetic mode..

Molecular salt effects in the gas phase: Tuning the kinetic basicity of [HCCLiCl]^- and [HCCMgCl2]^- by LiCl and MgCl2

GN Khairallah, G da Silva, RAJ O'Hair

2014-08-04

A combination of gas-phase ion-molecule reaction experiments and theoretical kinetic modeling is used to examine how a salt can in..

Unraveling organocuprate complexity: Fundamental insights into intrinsic group transfer selectivity in alkylation reactions

NJ Rijs, N Yoshikai, E Nakamura, RAJ O'Hair

2014-02-07

The near thermal conditions of an ion-trap mass spectrometer were used to examine the intrinsic gas-phase reactivity and selectivi..

Cobalt-mediated decarboxylative homocoupling of alkynyl carboxylic acids

MG Leeming, GN Khairallah, S Osburn, K Vikse, RAJ O'Hair

2014-01-01

Cobalt-mediated decarboxylative Glaser-like C-C bond coupling of carboxylates has been studied in the gas phase using collision-in..

Role of the metal, ligand, and alkyl/aryl group in the hydrolysis reactions of group 10 organometallic cations [(L)M(R)]

MJ Woolley, GN Khairallah, G Da Silva, PS Donnelly, BF Yates, RAJ O'Hair

2013-12-09

The reactions of water with the coordinatively unsaturated group 10 organometallic cations [(L)M(R)]⁺ (4; where L = 1,1..

Catalytic decarboxylative coupling of allyl acetate: Role of the metal centers in the organometallic cluster cations [CH3Cu 2] , [CH3AgCu] , and [CH 3Ag2]

H Al Sharif, KL Vikse, GN Khairallah, RAJ O'Hair

2013-10-14

Metal-catalyzed decarboxylative coupling reactions offer new opportunities for formation of C-C bonds. Here, multistage ion trap m..

CH and CC bond activation reactions in silver alkynyl cluster cations, RCCAg2

GN Khairallah, KA Saleeba, S Chow, W Eger, CM Williams, RAJ O'Hair

2013-08-30

A range of silver alkynyl cations RCCAg<inf>2</inf>⁺ (R = H, Me, Et, Pr, Bu, tBu and Ph) can be "synthesized" in the ga..

Fixed-charge phosphine ligands to explore gas-phase coinage metal-mediated decarboxylation reactions

K Vikse, GN Khairallah, JS McIndoe, RAJ O'Hair

2013-07-15

A combination of multistage mass spectrometry experiments and density functional theory (DFT) calculations were used to examine th..

sp–sp3 Coupling reactions of alkynylsilver cations, RC&≡CAg2 (R = Me and Ph) with allyliodide

GN Khairallah, CM Williams, S Chow, RAJ O'Hair

2013-06-12

Alkynylsilver cations, RC&≡CAg<inf>2</inf>⁺ (where R = Me and Ph) have been prepared in the gas phase using multistage ..

UV photodissociation action spectroscopy of haloanilinium ions in a linear quadrupole ion trap mass spectrometer

CS Hansen, BB Kirk, SJ Blanksby, RAJ O'Hair, AJ Trevitt

2013-06-01

UV-vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availabilit..

Gas-phase formation and fragmentation reactions of the organomagnesates [RMgX2]-

GN Khairallah, CCL Thum, D Lesage, JC Tabet, RAJ O'Hair

2013-04-22

A range of mononuclear organomagnesates [RMgX<inf>2</inf>]^- were generated in the gas phase by decarboxylation of the m..

Dimethylcuprate-catalyzed decarboxylative coupling of allyl acetate

NJ Rijs, RAJ O'Hair

2012-11-26

Allylic alkylation of organocuprates represents an important class of C-C bond forming reactions. A drawback of these reactions is..

Gas-phase unimolecular reactions of pallada- and nickelalactone anions

KL Vikse, GN Khairallah, RAJ O'Hair

2012-11-13

Electrospray ionization in combination with multistage mass spectrometry experiments in a linear ion trap mass spectrometer was us..

Theoretical approaches to estimating homolytic bond dissociation energies of organocopper and organosilver compounds

NJ Rijs, NJ Brookes, RAJ O'Hair, BF Yates

2012-09-06

Although organocopper and organosilver compounds are known to decompose by homolytic pathways among others, surprisingly little is..

Who wins: Pesci, peters, or deacon? Intrinsic reactivity orders for organocuprate formation via ligand decomposition

LOC Sraj, GN Khairallah, G Da Silva, RAJ O'Hair

2012-03-12

There are three metal-mediated ligand decomposition reactions that give rise to organometallics: (i) decarboxylation of a metal ca..

Gas-phase reactivity of group 11 dimethylmetallates with allyl iodide

NJ Rijs, N Yoshikai, E Nakamura, RAJ O'Hair

2012-02-08

Copper-mediated allylic substitution reactions are widely used in organic synthesis, whereas the analogous reactions for silver an..

Structural and photochemical properties of organosilver reactive intermediates MeAg 2 and PhAg 2

C Brunet, R Antoine, M Broyer, P Dugourd, A Kulesza, J Petersen, MIS Röhr, R Mitrić, V Bonačić-Koutecký, RAJ O'Hair

2011-08-25

Although there is growing interest in silver promoted carbon-carbon bond formation, a key challenge in developing robust and relia..

Modeling solvation of magnesium centers by ether ligands: Gas-phase synthesis and hydrolysis of the organomagnesium cations [CH3Mg(3 X -crown- X)] (X = 4-6)

MG Leeming, GN Khairallah, G Da Silva, RAJ O'Hair

2011-08-22

Gas-phase decarboxylation of the acetate ligand in the magnesium acetate crown complex cations [CH<inf>3</inf>CO<inf>2</inf>Mg(3X-..

Nitrogen adduction by three coordinate group 10 organometallic cations: Platinum is favoured over nickel and palladium

MJ Woolley, GN Khairallah, PS Donnelly, RAJ O'Hair

2011-07-30

Previous studies have shown that highly reactive product ions formed by collision-induced dissociation (CID) of precursor ions gen..