Synthese von Komplexen mit anomalen “protischen” N‐heterocyclischen Carbenen

Jin, Hua; Tan, Tristan Tsai Yuan; Hahn, F. Ekkehardt

doi:10.1002/ange.201507206

Cited by 14 publications

(1 citation statement)

References 61 publications

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“…Given the great and broad interest in organopalladium(IV) chemistry,w eb elieve this work will facilitate the synthetic and catalytic applications of the current [CC'C] pincer ligand as aC-donor-based platform. Research is currently underway to explore other possible methods [20] to access the Pd IV complexes reported herein and test other types of reactivity.…”

Section: Communicationsmentioning

confidence: 99%

Employing Aryl‐Linked Bis‐mesoionic Carbenes as a Pincer‐Type Platform to Access Ambient‐Stable Palladium(IV) Complexes

2019

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Section: Communicationsmentioning

confidence: 99%

Employing Aryl‐Linked Bis‐mesoionic Carbenes as a Pincer‐Type Platform to Access Ambient‐Stable Palladium(IV) Complexes

2019

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Employing Aryl‐Linked Bis‐mesoionic Carbenes as a Pincer‐Type Platform to Access Ambient‐Stable Palladium(IV) Complexes

2019

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The study of palladium(IV) species has great implications for PdII/PdIV‐mediated catalysis. However, most of the PdIV complexes rapidly decompose under ambient conditions, which makes the isolation, characterization and further reactivity study very challenging. The reported ancillary ligand platforms to stabilize PdIV species are dominated by chelating N‐donors such as bipyridines. In this work, we present two PdIV complexes with scarcely used C‐donors as the supporting platform. The anionic aryl donor and MIC (MIC=mesoionic carbene) are combined in a [CC′C]‐type pincer framework to access a series of ambient‐stable PdIV tris(halido) complexes. Their synthesis, solid‐state structures, stability, and reactivity are presented. To the best of our knowledge, the work presented herein reports the first isolated PdIV–MIC as well as the first PdIV carbene‐based aryl pincer.

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Preparation of Complexes Bearing N‐Alkylated, Anionic or Protic CAACs Through Oxidative Addition of 2‐Halogenoindole Derivatives

et al. 2020

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CAAC precursors 2‐chloro‐3,3‐dimethylindole 1 and 2‐chloro‐1‐ethyl‐3,3‐dimethylindolium tetrafluoroborate 2BF4 have been prepared and oxidatively added to [M(PPh3)4] (M=Pd, Pt). Salt 2BF4 reacts with [Pd(PPh3)4] in toluene at 25 °C over 4 days to yield complex cis‐[3]BF4 featuring an N‐ethyl substituted CAAC, two cis‐arranged phosphines and a chloro ligand. Compound trans‐[3]BF4 was obtained from the same reaction at 80 °C over 1 day. Salt 2BF4 reacts with [Pt(PPh3)4] to give cis‐[4]BF4. The neutral indole derivative 1 adds oxidatively to [Pt(PPh3)4] to give trans‐[5] featuring a CAAC ligand with an unsubstituted ring‐nitrogen atom. This nitrogen atom has been protonated with py⋅HBF4 to give trans‐[6]BF4 bearing a protic CAAC ligand. The PdII complex trans‐[7]BF4 bearing a protic CAAC ligand was obtained in a one‐pot reaction from 1 and [Pd(PPh3)4] in the presence of py⋅HBF4.

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Synthese von Komplexen mit anomalen “protischen” N‐heterocyclischen Carbenen

Cited by 14 publications

References 61 publications

Employing Aryl‐Linked Bis‐mesoionic Carbenes as a Pincer‐Type Platform to Access Ambient‐Stable Palladium(IV) Complexes

Employing Aryl‐Linked Bis‐mesoionic Carbenes as a Pincer‐Type Platform to Access Ambient‐Stable Palladium(IV) Complexes

Employing Aryl‐Linked Bis‐mesoionic Carbenes as a Pincer‐Type Platform to Access Ambient‐Stable Palladium(IV) Complexes

Preparation of Complexes Bearing N‐Alkylated, Anionic or Protic CAACs Through Oxidative Addition of 2‐Halogenoindole Derivatives

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