Anionische Palladium(0)‐ und Palladium(II)‐At‐Komplexe

Kolter, Marlene; Böck, Katharina; Karaghiosoff, Konstantin; Koszinowski, Konrad

doi:10.1002/ange.201707362

Cited by 13 publications

(1 citation statement)

References 65 publications

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“…For the case of palladate(0) anions, independent proof of the given assignments stems from the characterization of related complexes by ESI mass spectrometry. 22 For the products resulting from the reactions with PhI and other aryl halides, the situation is less clear. On the basis of quantum chemical calculations, Gooßen et al suggested that the intermediates directly formed in these reactions do not correspond to pentacoordinate palladium complexes inserted into the Ph−I bond (Scheme 5).…”

Section: Radiolytically or Photolytically Generated Organometallicsmentioning

confidence: 99%

Observation and Characterization of Single Elementary Reactions of Organometallics

Koszinowski

2024

Organometallics

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The diversity of organometallic reactivity can be traced back to relatively few elementary steps. Hence, a detailed knowledge of these elementary steps is essential for understanding the mechanism of organometallic reactions. Due to the complexity and heterogeneity of most organometallic reagents and catalysts, the observation and characterization of single elementary steps is challenging and requires special techniques. This tutorial presents and discusses different approaches how to probe individual elementary steps, including the analysis of stoichiometric reactions of preformed organometallics, the analysis of the reactivity of electrochemically, radiolytically, or photolytically generated organometallics, single-molecule techniques, experiments on surface-bound organometallic complexes and on organyl groups attached to metal surfaces, as well as gas-phase studies on mass-selected organometallic ions. The examples chosen for illustrating these methods chiefly examine the elementary steps of oxidative addition, transmetalation, and reductive elimination, all of which are of singular importance and together make up the catalytic cycle of transition-metal mediated cross-coupling reactions. Finally, the limitations of strategies focusing only on the analysis of single elementary steps without considering the complexity of the entire reactive system is addressed.

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Section: Radiolytically or Photolytically Generated Organometallicsmentioning

confidence: 99%

Observation and Characterization of Single Elementary Reactions of Organometallics

Koszinowski

2024

Organometallics

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Water and Sodium Chloride: Essential Ingredients for Robust and Fast Pd‐Catalysed Cross‐Coupling Reactions between Organolithium Reagents and (Hetero)aryl Halides

Dilauro¹,

Quivelli²,

Vitale³

et al. 2019

Angewandte Chemie

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Direct palladium‐catalysed cross‐couplings between organolithium reagents and (hetero)aryl halides (Br, Cl) proceed fast, cleanly and selectively at room temperature in air, with water as the only reaction medium and in the presence of NaCl as a cheap additive. Under optimised reaction conditions, a water‐accelerated catalysis is responsible for furnishing C(sp3)–C(sp2), C(sp2)–C(sp2), and C(sp)–C(sp2) cross‐coupled products, in competition with protonolysis, within a reaction time of 20 s, in yields of up to 99 %, and in the absence of undesired dehalogenated/homocoupling side products even when challenging secondary organolithiums serve as the starting material. It is worth noting that the proposed protocol is scalable and the catalyst and water can easily and successfully be recycled up to 10 times, with an E‐factor as low as 7.35.

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Palladium–Borane Cooperation: Evidence for an Anionic Pathway and Its Application to Catalytic Hydro‐/Deutero‐dechlorination

et al. 2019

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Metal–Lewis acid cooperation provides new opportunities in catalysis. In this work, we report a new type of palladium–borane cooperation involving anionic Pd0 species. The air‐stable DPB palladium complex 1 (DPB=diphosphine‐borane) was prepared and reacted with KH to give the Pd0 borohydride 2, the first monomeric anionic Pd0 species to be structurally characterized. The boron moiety acts as an acceptor towards Pd in 1 via Pd→B interaction, but as a donor in 2 thanks to B‐H‐Pd bridging. This enables the activation of C−Cl bonds and the system is amenable to catalysis, as demonstrated by the hydro‐/deutero‐dehalogenation of a variety of (hetero)aryl chlorides (20 examples, average yield 85 %).

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Anionische Palladium(0)‐ und Palladium(II)‐At‐Komplexe

Cited by 13 publications

References 65 publications

Observation and Characterization of Single Elementary Reactions of Organometallics

Observation and Characterization of Single Elementary Reactions of Organometallics

Water and Sodium Chloride: Essential Ingredients for Robust and Fast Pd‐Catalysed Cross‐Coupling Reactions between Organolithium Reagents and (Hetero)aryl Halides

Palladium–Borane Cooperation: Evidence for an Anionic Pathway and Its Application to Catalytic Hydro‐/Deutero‐dechlorination

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