Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes

Mikherdov, Alexander S.; Popov, Roman A.; Kinzhalov, Mikhail A.; Haukka, Matti; Polukeev, V. A.; Boyarskiy, Vadim P.; Roodt, Andreas

doi:10.1016/j.ica.2020.120012

Cited by 7 publications

(12 citation statements)

References 54 publications

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“…Previously, a similar kind of reversible formation of a cyclometalated carbene ligand was observed for mononuclear [25] and binuclear palladium complexes [12,26] …”

Section: Resultssupporting

confidence: 68%

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Pyridine‐2(1H)‐thione as a Bifunctional Nucleophile in Reaction with Pd^II and Pt^II Aryl Isocyanide Complexes

2022

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A method for obtaining C,S‐cyclometalated deprotonated diaminocarbene complexes via the addition of a bifunctional N,S‐nucleophile's endocyclic nitrogen atom to a coordinated isocyanide has been extended to the reactions with pyridine‐2(1H)‐thione. The coupling of PdII‐ and PtII‐bis(arylisocyanide) complexes with pyridine‐2(1H)‐thione leads to the formation of mononuclear C,S‐cyclometalated deprotonated diaminocarbene complexes in 90–96 % yield. The reaction proceeds via the initial coordination of the thione sulfur atom to the metal center followed by the intramolecular nucleophilic addition of the heterocyclic nitrogen atom to the metal‐ligated isocyanide carbon. Using an excess of pyridine‐2(1H)‐thione in this reaction leads to the formation of a mono‐C,S‐cyclometalated complex with a pendant mercaptopyridine ligand which is involved in the reversible intramolecular nucleophilic addition of the pyridine nitrogen to the isocyano carbon. The obtained complexes were characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopies, and single‐crystal X‐ray diffraction.

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“…Previously, a similar kind of reversible formation of a cyclometalated carbene ligand was observed for mononuclear [25] and binuclear palladium complexes [12,26] …”

Section: Resultssupporting

confidence: 68%

“…Previously, a similar kind of reversible formation of a cyclometalated carbene ligand was observed for mononuclear [25] and binuclear palladium complexes. [12,26] X-Ray Structures of complexes. The X-ray diffraction analysis was used to prove the structure of complexes 4 b, 5 b, 6 b, and 7 in the solid phase.…”

Section: Resultsmentioning

confidence: 99%

Pyridine‐2(1H)‐thione as a Bifunctional Nucleophile in Reaction with Pd^II and Pt^II Aryl Isocyanide Complexes

2022

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“…Apart from using carbene precursors, the preparations of metal acyclic carbene complexes from the metal-isocyanide precursors have been extensively reported. The nucleophilic attacks on the coordinated isocyanide carbon of metal isocyanide precursors with a suitable nucleophile, such as amines, [38][39][40][41][42][43][44][45] imines, 46,47 hydrazines 45,46 and alcohols, 48 give metal acyclic carbene complexes (Scheme 4). Based on the well-documented synthetic methodologies [49][50][51][52] and the rich coordination chemistry of isocyanide ligands, 53 a wide range of metal isocyanide complexes can be prepared.…”

Section: Nucleophilic Addition To Metal-isocyanide Precursorsmentioning

confidence: 99%

Transition-metal acyclic carbene complexes: building blocks for luminescent, stimuli-responsive, bioactive materials and catalysts

Chan

Chun

2023

Mater. Chem. Front.

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“…The best known types of CB involving S atoms are S•••N, S•••O, and S•••S interactions, which are often found both in biomolecules [10,32] and in organic [33][34][35] and coordination compounds [36][37][38]. Most of the examples described relate to the stabilization by CB of a certain conformation in intermediates or in starting compounds.…”

Section: Introductionmentioning

confidence: 99%

“…According to theoretical calculations, the reason for this transformation is that chalcogen bond S•••N in II is 1.8-2.3 kcal/mol more stable than chalcogen bond S•••Cl in I. The best known types of CB involving S atoms are S•••N, S•••O, and S•••S interactions, which are often found both in biomolecules [10,32] and in organic [33][34][35] and coordination compounds [36][37][38]. Most of the examples described relate to the stabilization by CB of a certain conformation in intermediates or in starting compounds.…”

Section: Introductionmentioning

confidence: 99%

Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)PdII Complexes

et al. 2023

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Binuclear diaminocarbene complexes, which form as a regioisomer mixture in the reaction between isocyanide–palladium(II) complex cis-[PdCl2(CNXyl)2] and 1,3-thiazol-2-amine, are able to exchange an anionic chloride ligand with other halides, such as Br or I. This process also affords binuclear complexes as mixtures of kinetically and thermodynamically controlled regioisomers. In CDCl3 solutions, we observed interconversion of kinetically and thermodynamically controlled regioisomers. The results of the DFT calculations revealed that in CHCl3 solution, each pair of the isomers exhibited two different types of chalcogen bonding such as S···X or S···N; the presence of CBs for two complexes in the solid state was also proven through X-ray crystallographic study. Based on the combined experimental and theoretical data, it could be concluded that thermodynamic favorability for the formation of thermodynamically controlled regioisomers increases in the Cl < Br ≈ I row and correlate well with the energy difference between S···N and S···X (X = Cl, Br, I) chalcogen bonds in kinetically and thermodynamically controlled products. This means that it is possible to change the structure of metallocycles in binuclear diaminocarbene complexes by simply replacing one halide ligand with another.

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Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes

Cited by 7 publications

References 54 publications

Pyridine‐2(1H)‐thione as a Bifunctional Nucleophile in Reaction with Pd^II and Pt^II Aryl Isocyanide Complexes

Pyridine‐2(1H)‐thione as a Bifunctional Nucleophile in Reaction with Pd^II and Pt^II Aryl Isocyanide Complexes

Transition-metal acyclic carbene complexes: building blocks for luminescent, stimuli-responsive, bioactive materials and catalysts

Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)PdII Complexes

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Reaction mechanism of regioisomerization in binuclear (diaminocarbene)PdII complexes

Cited by 7 publications

References 54 publications

Pyridine‐2(1H)‐thione as a Bifunctional Nucleophile in Reaction with PdII and PtII Aryl Isocyanide Complexes

Pyridine‐2(1H)‐thione as a Bifunctional Nucleophile in Reaction with PdII and PtII Aryl Isocyanide Complexes

Transition-metal acyclic carbene complexes: building blocks for luminescent, stimuli-responsive, bioactive materials and catalysts

Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)PdII Complexes

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Pyridine‐2(1H)‐thione as a Bifunctional Nucleophile in Reaction with Pd^II and Pt^II Aryl Isocyanide Complexes

Pyridine‐2(1H)‐thione as a Bifunctional Nucleophile in Reaction with Pd^II and Pt^II Aryl Isocyanide Complexes