Gas phase synthesis and reactivity of dimethylaurate

Rijs, Nicole J.; Sanvido, Gustavo Braga; Khairallah, George N.; O’Hair, Richard A. J.

doi:10.1039/c0dt00508h

Cited by 35 publications

(51 citation statements)

References 57 publications

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“…While all metals underwent bond homolysis (eq 3a), 6e and to a lesser extent gold, 8 also fragmented via a novel 1,2-dyotropic rearrangement reaction (eqs 3b and 3c), in which both methyl groups underwent dehydro C−C bond coupling. Dimethylcuprate has been shown to be more reactive in C−C bond coupling reactions with methyl iodide 6a and allyl iodide.…”

Section: And 2a) Andmentioning

confidence: 99%

Gas-Phase Unimolecular Reactions of Pallada- and Nickelalactone Anions

2012

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Electrospray ionization in combination with multistage mass spectrometry experiments in a linear ion trap mass spectrometer was used to generate and study the gasphase ion chemistry of the metallalactones [(CH 3 CO 2 )Ni-(CH 2 CO 2 )] − (m/z 175, 5a) and [(CH 3 CO 2 )Pd(CH 2 CO 2 )] − (m/z 223, 5b). Low-energy collision-induced dissociation (CID) resulted in decarboxylation to produce novel organometallic ions at m/z 131 (Ni) and m/z 179 (Pd). Isotope labeling experiments, bimolecular gas-phase reactions with allyl iodide, and DFT calculations reveal that decarboxylation primarily occurs from the acetato ligand to yield ions of the form [(CH 3 )M(CH 2 CO 2 )] − (M = Pd, Ni). Further CID experiments on [(CH 3 )M(CH 2 CO 2 )] − together with DFT calculations highlight the following. (1) Both palladium and nickel can facilitate C−C bond formation, with elimination of ethylene being observed.(2) The mechanism for formation of ethylene from [(CH 3 )M(CH 2 CO 2 )] − is inherently different for M = Pd versus M = Ni. Elimination of ethylene is competitive with further decarboxylation in the case of nickel, and nickel remains in the 2+ oxidation state throughout. In contrast, the palladium complex is reduced to palladium(0) upon C−C bond formation and undergoes a second decarboxylation before ethylene is released. Finally, the products of the ion−molecule reactions of [(CH 3 )Pd(CH 2 CO 2 )] − (7b) with allyl iodide provide evidence for the formation of the Pd(IV) intermediate [(CH 3 )(I)-(CH 2 CHCH 2 )Pd(CH 2 CO 2 )] − , which decomposes via a range of processes, including losses of iodide, propionate, allyl, and methyl radicals and reductive elimination of butane and methyl iodide.

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Section: And 2a) Andmentioning

confidence: 99%

Gas-Phase Unimolecular Reactions of Pallada- and Nickelalactone Anions

2012

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“…Concerning the reactionm echanism, it is interesting to note that the process requires4days for completion in the dark, while it proceeds quantitatively in just 10 min when exposed to daylight, as determined by 19 FNMR spectroscopy.T he sharp rate difference observed upon photoirradiation is clear evidence that the reaction proceeds by ar adicalm echanism, as also found in relateds ystems. [18] The AX 3 Ys toichiometry of the obtaineda nion precludesa ny decision concerning the stereochemistry of the process.However,when the reactioniscarried out under similar conditions using nBu F Ia st he reagent, the trans isomer of [PPh 4 ][nBu F (CF 3 ) 2 AuI] (2)i ss tereoselectively ob-tained (Scheme 1; Figure S1).…”

Section: Synthesis Of [Pph 4 ][(Cf 3 ) 3 Aui] (1)mentioning

confidence: 99%

“…[14] The clean behavior now observed for the fluorinated [CF 3 AuCF 3 ] À speciest owards RI reagents (Scheme 1) is in sharp contrastw ith that previously reported fort he non-fluorinated [CH 3 AuCH 3 ] À homologue. [19] Actually,w ea re not aware of the existence of any simple anionic [(CH 3 ) 3 AuX] À species.I nc ontrast, the fluorinated (CF 3 ) 3 Au fragment can be stabilized not only by iodide, but also by any other halogenl igand,asw ew ill see next. [9c] Although the [(CH 3 ) 3 AuI] À anion might, in principle, be involved in the referred process, this nonfluorinated anion has not been isolated or identified to date.…”

Section: Synthesis Of [Pph 4 ][(Cf 3 ) 3 Aui] (1)mentioning

confidence: 99%

“…Valuable structurali nformation in solution is provided by 19 FNMR spectroscopy.O ur results validate previous assignments to the [(CF 3 ) 3 AuX] À anions detectedi ns olution (X = F, Cl, CN). Valuable structurali nformation in solution is provided by 19 FNMR spectroscopy.O ur results validate previous assignments to the [(CF 3 ) 3 AuX] À anions detectedi ns olution (X = F, Cl, CN).…”

Section: Synthesis and Characterization Of Further Anionicderivativesmentioning

confidence: 99%

“…The resultsa re given in the Supporting Information (Figures S10-S14). Once the decomposition temperature was determined by TGA/DTA,t he halide compounds were thermolyzed in sealed tubes under an inert atmosphere (Ar), and their decomposition products were analyzed by 19 FNMR spectroscopy with the aid of MS. The most stable speciesi st he cyano-derivative 6,w hich decomposesa t3 50 8C.…”

Section: Thermolyses In the Condensed Phasementioning

confidence: 99%

See 2 more Smart Citations

Anionic Derivatives of Perfluorinated Trimethylgold

Pérez‐Bitrián

Martínez-Salvador

Baya

et al. 2017

Chemistry A European J

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The homoleptic compound [PPh4][CF3AuCF3] cleanly undergoes photoinduced oxidative addition of CF3I to afford the organogold(III) derivative [PPh4][(CF3)3AuI] in good yield and under mild conditions. This compound provides a convenient entry to the chemistry of the perfluorinated (CF3)3Au fragment, the properties of which were analyzed with the aid of DFT methods and compared with those of the homologous non‐fluorinated (CH3)3Au moiety. It was found that reductive elimination of CX3−CX3 in the former (X=F) requires a much higher energy barrier than in the latter (X=H) and is therefore considerably less favored. This can be considered as one of the main features underlying the significantly higher stability associated to the (CF3)3Au fragment and its derivatives. This unsaturated, 14‐electron species can be stabilized by coordination of any of the halide ligands, including fluoride. In fact, the whole series of anionic [PPh4][(CF3)3AuX] complexes (X=F, Cl, Br, I, CN) has now been isolated and conveniently characterized. Evidence for intermolecular decomposition pathways upon thermolysis in the condensed phase is presented.

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Mass Spectrometry of Organogold Compounds

O’Hair

2015

Patai's Chemistry of Functional Groups

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The use of mass spectrometry (MS) based methods in organogold chemistry is reviewed. The focus is on both fundamental gas‐phase ion chemistry studies in which the mass spectrometer is used as a “gas‐phase reactor” and the analytical applications of mass spectrometry. For the former, the topics covered include: thermochemical measurements (bond energies from reactions of Au + with substrates and Au + and R 3 PAu + affinities); photoelectron, IR and UV‐Vis spectroscopy; ion‐molecule reactions of bare Au + , ligated Au(L) n + , Au − and gold clusters with substrates; formation and reactions of organogold ions. The latter includes a discussion on: the use of different ionization methods (electron ionization, fast‐atom bombardment, electrospray ionization and matrix assisted laser desorption ionization) in the analysis of gold compounds; the use of MS in the bioinorganic chemistry of gold; MS‐based studies of relevance to catalysis.

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Gas phase synthesis and reactivity of dimethylaurate

Cited by 35 publications

References 57 publications

Gas-Phase Unimolecular Reactions of Pallada- and Nickelalactone Anions

Gas-Phase Unimolecular Reactions of Pallada- and Nickelalactone Anions

Anionic Derivatives of Perfluorinated Trimethylgold

Mass Spectrometry of Organogold Compounds

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