Photoelectron imaging and theoretical study on the structure and chemical binding of the mixed-ligand M(I) complexes, [HMSH]− (M = Cu, Ag, and Au)

Collision-induced dissociation is carried out for electrosprayed [Fe·GlyGlyHis-H], [Ni·GlyGlyHis-H], [Cu·GlyGlyHis-H], and [Zn·GlyGlyHis-H] complexes. [Fe·GlyGlyHis-H], [Ni·GlyGlyHis-H], and [Zn·GlyGlyHis-H] yield metal-bound peptide sequence ions and dehydrated ions as primary products, whereas [Cu·GlyGlyHis-H] generates a more extensive series of metal-bound sequence ions and a product arising from the unusual loss of a formaldehyde moiety; dehydration is significantly suppressed for this complex. Density functional theory calculations show that the copper ion-deprotonated peptide binding energy is substantially higher than those in other complexes, suggesting that there is a correlation between ion-ligand binding energy and their fragmentation behavior.

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“…Photoelectron imaging would provide an insight into the nature of interactions between metal ions and biomolecular ligands in the gas phase. 27…”

Section: Dft Calculations Of [Máglyglyhis-h] þmentioning

confidence: 99%

Investigation of collision-induced dissociation products and structures of gas-phase [M·GlyGlyHis-H]⁺ (M = Fe, Ni, Cu, and Zn) complexes

Gannamani

Shin

2017

Eur J Mass Spectrom (Chichester)

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“…[ 63 CuH 2 ] − reacts with 1-butanethiol (ΔH acid = 353.7 kcal mol −1 ) 39 at the collision rate 40 to give [ 63 CuH(S(CH 2 ) 3 CH 3 )] − (m/z 153) 41 and H 2 (Figure S13a, eq 36). The reaction of [ 63 CuHD] − with 1-butanethiol (Figure S14) produced [ 63 CuH-(S(CH 2 ) 3 CH 3 )] − (eq 37) and [ 63 CuD(S(CH 2 ) 3 CH 3 )] − (eq 38, Figure S14), giving a KIE of 0.86, which is comparable to that of 2,2,2-trifluoroethanol.…”

mentioning

confidence: 99%

Gas-Phase Ion–Molecule Reactions of Copper Hydride Anions [CuH₂]⁻ and [Cu₂H₃]⁻

et al. 2017

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Gas-phase reactivity of the copper hydride anions [CuH] and [CuH] toward a range of neutral reagents has been examined via multistage mass spectrometry experiments in a linear ion trap mass spectrometer in conjunction with isotope labeling studies and Density Functional Theory (DFT) calculations. [CuH] is more reactive than [CuH], consistent with DFT calculations, which show it has a higher energy HOMO. Experimentally, [CuH] was found to react with CS via hydride transfer to give thioformate (HCS) in competition with the formation of the organometallic [CuCS] ion via liberation of hydrogen; CO via insertion to produce [HCuOCH]; methyl iodide and allyl iodide to give I and [CuHI]; and 2,2,2-trifluoroethanol and 1-butanethiol via protonation to give hydrogen and the product anions [CuH(OCHCF)] and [CuH(SBu)]. In contrast, the weaker acid methanol was found to be unreactive. DFT calculations reveal that the differences in reactivity between CS and CO are due to the lower lying π* orbital of the former, which allows it to accept electron density from the Cu center to form the initial three-membered ring complex intermediate, [HCu(η-CS)]. In contrast, CO undergoes the barrierless side-on hydride transfer promoted by the high electronegativity of the oxygen atoms. Side-on S2 mechanisms for reactions of [CuH] with methyl iodide and allyl iodide are favored on the basis of DFT calculations. Finally, the DFT calculated barriers for protonation of [CuH] by methanol, 2,2,2-trifluoroethanol, and 1-butanethiol correlate with their gas-phase acidities, suggesting that reactivity is mainly controlled by the acidity of the substrate.

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Synthesis, characterization, luminescent properties of silver (I) complexes based on organic P-donor ligands and mercaptan ligands

et al. 2017

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Photoelectron imaging and theoretical study on the structure and chemical binding of the mixed-ligand M(I) complexes, [HMSH]− (M = Cu, Ag, and Au)

Cited by 4 publications

References 58 publications

Investigation of collision-induced dissociation products and structures of gas-phase [M·GlyGlyHis-H]⁺ (M = Fe, Ni, Cu, and Zn) complexes

Investigation of collision-induced dissociation products and structures of gas-phase [M·GlyGlyHis-H]⁺ (M = Fe, Ni, Cu, and Zn) complexes

Gas-Phase Ion–Molecule Reactions of Copper Hydride Anions [CuH₂]⁻ and [Cu₂H₃]⁻

Synthesis, characterization, luminescent properties of silver (I) complexes based on organic P-donor ligands and mercaptan ligands

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Photoelectron imaging and theoretical study on the structure and chemical binding of the mixed-ligand M(I) complexes, [HMSH]− (M = Cu, Ag, and Au)

Cited by 4 publications

References 58 publications

Investigation of collision-induced dissociation products and structures of gas-phase [M·GlyGlyHis-H]+ (M = Fe, Ni, Cu, and Zn) complexes

Investigation of collision-induced dissociation products and structures of gas-phase [M·GlyGlyHis-H]+ (M = Fe, Ni, Cu, and Zn) complexes

Gas-Phase Ion–Molecule Reactions of Copper Hydride Anions [CuH2]− and [Cu2H3]−

Synthesis, characterization, luminescent properties of silver (I) complexes based on organic P-donor ligands and mercaptan ligands

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Investigation of collision-induced dissociation products and structures of gas-phase [M·GlyGlyHis-H]⁺ (M = Fe, Ni, Cu, and Zn) complexes

Investigation of collision-induced dissociation products and structures of gas-phase [M·GlyGlyHis-H]⁺ (M = Fe, Ni, Cu, and Zn) complexes

Gas-Phase Ion–Molecule Reactions of Copper Hydride Anions [CuH₂]⁻ and [Cu₂H₃]⁻