Carboxylate-assisted C–H activation of phenylpyridines with copper, palladium and ruthenium: a mass spectrometry and DFT study

Gray, Andrew; Tsybizova, Alexandra; Roithová, Jana

doi:10.1039/c5sc01729g

Cited by 47 publications

(47 citation statements)

References 94 publications

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“…This study aimed to assess the role of β ‐diketonate in 2‐phenylpyridine C–H activation. In principle, the β ‐diketonate ligand could accept the proton from a C–H activated bond in a mechanism similar to those reported for ruthenium carboxylates …”

Section: Introductionmentioning

confidence: 58%

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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: Introductionmentioning

confidence: 58%

“…Transition states for the ruthenium(II)‐catalysed C–H activation of a 2‐phenylpyridine with a different ligand coordinated to ruthenium: a) imidazolium salt and carbonate, b) carboxylate and c) phosphinoate …”

Section: Introductionmentioning

confidence: 99%

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

2018

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“…The IRMPD spectrum of the model complex [(2‐PhPy)2Pd(OAc)] + shows signatures of both bidentate and monodentate coordination of acetate . Thus, the spectrum shows a mixture of ions with intact 2‐phenylpyridine ligands and ions with one C−H activated molecule of 2‐phenylpyridine.…”

Section: Metal Complexesmentioning

confidence: 99%

“…2‐Phenylpyridine (2‐PhPy) is an example of such a system. Palladium acetate coordinates to the nitrogen atom of 2‐phenylpyridine (Figure b) . The acetate ligand deprotonates the ortho ‐carbon atom of the phenyl ring via a six‐membered transition structure (Figure c).…”

Section: Metal Complexesmentioning

confidence: 99%

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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“…The presence of weakly donating carboxylates is likely to increase the electrophilicity of the metal center [207,208]. Fluorinated analogues (2-9) of carboxylato/carbonyl compounds were also studied for cyclopropanation reaction.…”

Section: Alcohol Dehydrogenation At Axial Site Of a [Ru I -Ru I ] Bondmentioning

confidence: 99%

Homo- and Heterobimetallic Complexes in Catalysis

Kalck¹

2016

Topics in Organometallic Chemistry

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Carboxylate-assisted C–H activation of phenylpyridines with copper, palladium and ruthenium: a mass spectrometry and DFT study

Abstract: The transition state of metal carboxylate mediated C–H activation is associated with carbon–metal bond formation supported by electron-poor carboxylates.

Cited by 47 publications

References 94 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

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

Homo- and Heterobimetallic Complexes in Catalysis

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