Gas-phase study of metal complexes with redox-active ligands

Yassaghi, Ghazaleh; Jašíková, Lucie; Roithová, Jana

doi:10.1016/j.ijms.2016.07.010

Cited by 13 publications

(12 citation statements)

References 42 publications

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“…However, no [( β ‐diketonate)H] elimination is observed, thus suggesting that C–H activation does not proceed within the gaseous [Ru(CYM)( β ‐diketonate)(PhPy)] + reaction complex; otherwise, C–H activation would have been evident as the elimination of neutral [( β ‐diketonate)H]. We can estimate the binding energy of 2‐phenylpyridine to the ruthenium center from energy‐resolved CID experiments (Figure b), because the collision energy scale of our ion trap instrument can be calibrated (Figure S5 in the Supporting Information) . We assessed the appearance energy for the loss of PhPy as 1.6 ± 0.1 eV by linear extrapolation of the 2‐phenylpyridine appearance curve (Figure b).…”

Section: Resultsmentioning

confidence: 95%

C–H Bond Activation by a Ruthenium(II) β‐Diketonate Complex: A Mechanistic Study

2018

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Ruthenium(II)‐catalysed C–H bond activation of arenes containing a functional directing group depends on the ligand coordinated to ruthenium(II). In this study, 2‐phenylpyridine C–H activation catalysed by a “piano‐stool“ ruthenium(II) complex containing a fluorinated β‐diketonate ligand was examined by ESI‐MS in combination with CID experiments. [Ru(β‐diketonate)(CTPhPy)Cl]+ was identified as an active intermediate, and its collisional activation leads to C–H activation. CID analysis indicates proton transfer from the phenylpyridine to the chlorine anion, showing HCl elimination, while the β‐diketonate ligand is retained in the complex together with the activated phenylpyridine. Furthermore, DFT calculations were performed for the neutral analogue [Ru(β‐diketonate)(PhPy)Cl] to identify all ruthenium intermediates along the C–H activation reaction pathway. The results suggest that the most stable structure of [Ru(β‐diketonate)(PhPy)Cl] has pre‐activated 2‐phenylpyridine with a partly developed Ru–H bond. Further, we show that K2CO3 is not directly involved in the C–H activation step and it serves in the reaction as a base.

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Section: Resultsmentioning

confidence: 95%

C–H Bond Activation by a Ruthenium(II) β‐Diketonate Complex: A Mechanistic Study

2018

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“…The species of interest are formed in the gas-phase and are not amenable to an inquiry by standard spectroscopy methods for radical species, such as EPR spectroscopy. However, gaseous ions may be assayed by IR multiple photon dissociation (IRMPD) spectroscopy in combination with theoretical methods, as reported, inter alia, in the analysis of metal complexes with non-innocent ligands, [21][22][23] as well as in the discrimination between different spin-states of iron(IV) oxo complexes. [24] Therefore, IRMPD spectroscopy is promising for the characterization of the effective oxidation state of platinum.…”

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Can an Elusive Platinum(III) Oxidation State be Exposed in an Isolated Complex?

et al. 2020

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Platinum(IV) complexes are extensively studied for their activity against cancer cells as potential substitutes for the widely used platinum(II) drugs. PtIV complexes are kinetically inert and need to be reduced to PtII species to play their pharmacological action, thus acting as prodrugs. The mechanism of the reduction step inside the cell is however still largely unknown. Gas‐phase activation of deprotonated platinum(IV) prodrugs was found to generate products in which platinum has a formal +3 oxidation state. IR multiple photon dissociation spectroscopy is thus used to obtain structural information helping to define the nature of both the platinum atom and the ligands. In particular, comparison of calculations at DFT, MP2 and CCSD levels with experimental results demonstrates that the localization of the radical is about equally shared between the dxz orbital of platinum and the pz of nitrogen on the amino group, the latter acting as a non‐innocent ligand.

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“…Quinones can accept two electrons stepwise, sequentially forming semiquinones and diol–diates. This behaviour was studied for ortho ‐quinone phenanthraquinone (PQ) in complexes with sodium, copper and iron (Figure ) . The sodium cation can only be in the +I oxidation state.…”

Section: Metal Complexesmentioning

confidence: 99%

“…This behaviour was studied for ortho-quinone phenanthraquinone (PQ) in complexes with sodium,c oppera nd iron ( Figure 12). [36,37] The sodium cation can only be in the + Io xi-dation state. Accordingly,t he binding in the [(PQ) 2 Na] + complex is dominated by ion-dipole interactions.T he C=Os tretching band of [(PQ) 2 Na] + is found at 1670cm À1 .C opper(I) in the analogousc omplex [(PQ) 2 Cu] + is redox active and can be oxidised.C opper oxidation requires PQ reduction to the semiquinone form.…”

Section: Metal Complexes With Redox Active Ligandsmentioning

confidence: 99%

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Infrared Multiphoton Dissociation Spectroscopy with Free‐Electron Lasers: On the Road from Small Molecules to Biomolecules

Jašíková

Roithová

2018

Chemistry A European J

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Infrared multiphoton dissociation (IRMPD) spectroscopy is commonly used to determine the structure of isolated, mass-selected ions in the gas phase. This method has been widely used since it became available at free-electron laser (FEL) user facilities. Thus, in this Minireview, we examine the use of IRMPD/FEL spectroscopy for investigating ions derived from small molecules, metal complexes, organometallic compounds and biorelevant ions. Furthermore, we outline new applications of IRMPD spectroscopy to study biomolecules.

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Gas-phase study of metal complexes with redox-active ligands

Cited by 13 publications

References 42 publications

C–H Bond Activation by a Ruthenium(II) β‐Diketonate Complex: A Mechanistic Study

C–H Bond Activation by a Ruthenium(II) β‐Diketonate Complex: A Mechanistic Study

Can an Elusive Platinum(III) Oxidation State be Exposed in an Isolated Complex?

Infrared Multiphoton Dissociation Spectroscopy with Free‐Electron Lasers: On the Road from Small Molecules to Biomolecules

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