Forming trifluoromethylmetallates: competition between decarboxylation and C–F bond activation of group 11 trifluoroacetate complexes, [CF3CO2ML]−

Rijs, Nicole J.; O’Hair, Richard A. J.

doi:10.1039/c2dt12117d

Cited by 51 publications

(53 citation statements)

References 94 publications

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“…Unfortunately, CID experiments revealed that instead of decarboxylation occurring, all of these complexes fragmented to produce [(phen)Ni(X)] + as the sole CID product (data not shown). These reactions are likely to proceed via similar C―X bond activation mechanisms found for losses of CF 2 CO 2 from the coinage metal trifluoroacetates, [(CF 3 CO 2 ) 2 M] − (where M = Cu, Ag, and Au) …”

Section: Resultsmentioning

confidence: 89%

Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

et al. 2019

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Gas‐phase C―C coupling reactions mediated by Ni (II) complexes were studied using a linear quadrupole ion trap mass spectrometer. Ternary nickel cationic carboxylate complexes, [(phen)Ni (OOCR1)]+ (where phen = 1,10‐phenanthroline), were formed by electrospray ionization. Upon collision‐induced dissociation (CID), they extrude CO2 forming the organometallic cation [(phen)Ni(R1)]+, which undergoes gas‐phase ion‐molecule reactions (IMR) with acetate esters CH3COOR2 to yield the acetate complex [(phen)Ni (OOCCH3)]+ and a C―C coupling product R1‐R2. These Ni(II)/phenanthroline‐mediated coupling reactions can be performed with a variety of carbon substituents R1 and R2 (sp3, sp2, or aromatic), some of them functionalized. Reaction rates do not seem to be strongly dependent on the nature of the substituents, as sp3‐sp3 or sp2‐sp2 coupling reactions proceed rapidly. Experimental results are supported by density functional theory calculations, which provide insights into the energetics associated with the C―C bond coupling step.

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Section: Resultsmentioning

confidence: 89%

Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

et al. 2019

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“…The difference between the previous studies and this work is that the α-lactone formed upon fragmentation chargeremote fragmentation of PheSO 3 À is ionic, and therefore detectable by mass spectrometry. Previous studies of halogenated carboxylates [48][49][50][51] have inferred α-lactone structures based on the observation of halide products.…”

Section: Resultsmentioning

confidence: 99%

Mass spectrometric study of the decomposition pathways of canonical amino acids and α‐lactones in the gas phase

Koirala

Kodithuwakkuge

Wenthold

2015

J of Physical Organic Chem

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The dissociation pathways of a gas‐phase amino acid with a canonical (non‐zwitterionic) α‐amino acid moiety are studied by using mass spectrometry. Investigation of the canonical amino acid moiety is possible because the ionized amino acid, a sulfonated phenylalanine, has a charge center that is separated from the amino acid, and dissociation occurs by charge‐remote fragmentation. The amino acid is found to dissociate only by loss of NH3 upon collision‐induced dissociation to form a substituted α‐lactone. The dissociation is consistent with what has been observed previously upon pyrolysis of other α‐substituted carboxylic acids. Decarboxylation, which has also been reported previously for amino acid pyrolysis, is not observed, likely because the product would be a high‐energy, ammonium ylide. The resulting α‐lactone is found to undergo dissociation by decarbonylation to give an aldehyde, and by loss of CO2. Decarboxylation is calculated to occur through a transition state involving hydride shift coupled with lactone ring‐opening. The transition state is found to be stabilized by the negative charge, and therefore, decarboxylation is more favorable for anions. The results show that remote ionic groups can be used as mostly inert charge carriers to enable mass spectrometry to be used to investigate the gas‐phase physical and chemical properties of different types of functional groups, including amino acids. Copyright © 2015 John Wiley & Sons, Ltd.

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“…[11a] Virtually identical average AuÀF interatomic distances were found in the neutral metallacyclic difluorides (N^C)AuF 2 (198.2(4) pm av.). By far the most favored process involves CF 2 extrusion [14] and formation of the trifluoride complex [CF 3 AuF 3 ] À with no change in the metal oxidation state (Scheme 2a). It undergoes various collision-induced dissociation processes (Figures S8-S12), which are summarized in Scheme 2.…”

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An Organogold(III) Difluoride with a trans Arrangement

et al. 2018

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The trans isomer of the organogold(III) difluoride complex [PPh ][(CF ) AuF ] has been obtained in a stereoselective way and in excellent yield by reaction of [PPh ][CF AuCF ] with XeF under mild conditions. The compound is both thermally stable and reactive. Thus, the fluoride ligands are stereospecifically replaced by any heavier halide or by cyanide, the cyanide affording [PPh ][trans-(CF ) Au(CN) ]. The organogold fluoride complexes [CF AuF ] (x=1, 2, 3) have been experimentally detected to arise upon collision-induced dissociation of the [trans-(CF ) AuF ] anion in the gas phase. Their structures have been calculated by DFT methods. In the isomeric forms identified for the open-shell species [CF AuF ] , the spin density residing on the metal center is found to strongly depend on the precise stereochemistry. Based on crystallographic evidence, it is concluded that Au and Ag have similar covalent radii, at least in their most common square-planar geometry.

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Forming trifluoromethylmetallates: competition between decarboxylation and C–F bond activation of group 11 trifluoroacetate complexes, [CF3CO2ML]−

Cited by 51 publications

References 94 publications

Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

Mass spectrometric study of the decomposition pathways of canonical amino acids and α‐lactones in the gas phase

An Organogold(III) Difluoride with a trans Arrangement

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