Synthesis and reactivity of thiosemicarbazone palladacycles. Crystal structure analysis and theoretical calculations

Martı́nez, Javier; Cabaleiro‐Lago, Enrique M.; Ortigueira, Juan M.; Pereira, Miguel Pérez; Frieiro, Pablo; Lucio, Fátima; Vila, José M.

doi:10.1016/j.ica.2016.03.044

Cited by 12 publications

(8 citation statements)

References 30 publications

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“…The sum of angles about palladium atom is approximately 360˚. Pd1-N1 2.029(3) Å, Pd1-C1 2.048(3) Å and Pd1-S1 2.3351(13) Å bond distances are within the expected range, and they are in agreement with similar structures previously presented by us [12][13][14]. Intramolecular π-π stacking interactions were observed between two phenyl rings, one from each phosphorus atom (see Figure 4c).…”

Section: Single Crystal X-ray Diffractionsupporting

confidence: 88%

Synthesis and X-ray Diffraction Study of thiosemicarbazone Palladacycles with dppm

Rúa‐Sueiro

Munín‐Cruz

Reigosa

et al. 2021

The 2nd International Online Conference on Crystals

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Cyclometallated compounds have been extensively studied, in particular those with palladium and platinum. This is because of their possible applications in medicinal chemistry, as anticancer or antimicrobial agents; in some cases, with similar results as cisplatin, carboplatin or oxaliplatin. What is also remarkable is their use as homogeneous catalysts, for example, in cross coupling reactions such as Suzuki–Miyaura or Mizoroki–Heck. Herein, we report the synthesis of different thiosemicarbazone ligands, which will be reacted with a palladium or platinum salt, to give the corresponding cyclometallated compounds; in addition, their reactivity with bis(diphenylphosphino)methane (dppm) will be studied. Characterization has been carried out by elemental analysis, IR spectroscopy, 1H and 31P NMR spectroscopy. Additionally, 1c has been studied by X-ray diffraction.

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Section: Single Crystal X-ray Diffractionsupporting

confidence: 88%

Synthesis and X-ray Diffraction Study of thiosemicarbazone Palladacycles with dppm

Rúa‐Sueiro

Munín‐Cruz

Reigosa

et al. 2021

The 2nd International Online Conference on Crystals

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“…This κ 3 ‐SNS coordination bears strong similarity to the Pt and Pd coordination complexes reported by Bowman‐James and co‐workers, which contained a similar ligand back‐bone. Numerous thiosemicarbazones coordinated to Pd(II), illustrates bridging S–Pd bonds which stabilizes the coordinatively unsaturated Pd(II). A similar scenario is possible with pdcta due to the (N=C–S – ) 2 form of pdcta in the metal complex.…”

Section: Resultsmentioning

confidence: 99%

SNS versus SNN Pincer Ligands: Electrochemical Studies and Their Palladium(II) Complexes as Electro‐Catalyst for Proton Reduction

Lawrence

Mulder

2018

ChemistrySelect

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Electrochemical measurements on pincer ligands bis‐N‐(2,5‐dimethoxyphenyl)pyridine‐2,6‐dicarbothioamide (pdcta) and 6‐(4,7‐dimethoxy‐2‐benzothiazolyl)‐N‐(2,5‐dimethoxyphenyl)‐2‐pyridinecarbothioamide (pbcta) in N,N‐dimethylformamide (DMF) and dimethylsulfoxide (DMSO) on a glassy carbon working electrode revealed sulfur centred electrochemical processes. Spectroscopic, elemental and electrochemical analyses indicated that pdcta coordinated to Pd(II) via a κ3‐SNS mode to give 1 whereas pbcta coordinated via a κ3‐SNN mode to give 2. Electrochemical measurements in DMF indicated that the reduction of Pd(II)→Pd(0) proceeded in a concerted manner in the 2, whereas reduction was resolved into the Pd(II)→Pd(I)→Pd(0) in the case of 1. In the presence of p‐toluenesulfonic acid, both palladium complexes displayed electro‐catalytic proton reduction in DMF, with associated overpotentials calculated to be 97 mV and 156 mV for 1 and 2, respectively. The data suggests that the κ3‐SNS pincer ligand enhances the activity of the Pd(II) towards proton reduction relative to 1.

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“…To study the reactivity of these compounds the diphosphine, dppm, was chosen. The reaction was performed according to the literature procedure [7] to give a mononuclear compound (Scheme 3). The compounds c1-c3 were satisfactorily characterized by elemental analysis, 1 H-NMR and 31 P-{ 1 H}-NMR.…”

Section: Study the Reactivity Of Cyclometallated Compound With Diphosmentioning

confidence: 99%

Preparation of novel complexes bearing diphosphine (dppm) derived from thiosemicarbazone palladacycles

Bermudez

Diz-Gil

Munín‐Cruz

et al. 2020

Proceedings of the 24th International Electronic Conference on Synthetic Organic Chemistry

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The synthesis of palladium cyclometallated compounds with thiosemicarbazone ligands is described, as well as their reactivity with bidentate phosphine ligands. The synthesis of the ligands was carried out by a condensation reaction between a ketone and a thiosemicarbazide. Subsequently, metalation proceeds and the resulting product is reacted with bis(diphenylphosphino)methane (dppm) under the appropriate conditions to yield the compound with monocoordinated diphosphine.

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Synthesis and reactivity of thiosemicarbazone palladacycles. Crystal structure analysis and theoretical calculations

Cited by 12 publications

References 30 publications

Synthesis and X-ray Diffraction Study of thiosemicarbazone Palladacycles with dppm

Synthesis and X-ray Diffraction Study of thiosemicarbazone Palladacycles with dppm

SNS versus SNN Pincer Ligands: Electrochemical Studies and Their Palladium(II) Complexes as Electro‐Catalyst for Proton Reduction

Preparation of novel complexes bearing diphosphine (dppm) derived from thiosemicarbazone palladacycles

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