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Phosphino hydrazones represent a versatile class of nitrogen‐containing phosphine ligands. Herein, we report a modular synthesis of phosphino hydrazone ligands by hydrazone condensation reaction of three different aryl hydrazines with 3‐(diphenylphosphino)propanal (PCHO). Complexation reactions of these phosphino hydrazone ligands with palladium(II) and platinum(II) were investigated and the catalytic activity of the palladium(II) complexes was explored in a Cu‐free Sonogashira cross‐coupling reaction achieving yields up to 96 %. Additionally it was shown that the catalytically active species is homogeneous. [ABSTRACT FROM AUTHOR]

The syntheses of the first B9‐connected carboranylphosphines (B9‐Phos) featuring two carboranyl moieties as well as access to B9‐Phos ligands with bulky electron‐donating substituents, previously deemed unattainable, is reported. The electrochemical properties of the B9‐Phos ligands were investigated, revealing the ability of the mesityl derivatives to form stabilized phosphoniumyl radical cations. The B9‐Phos ligands display an extremely electron‐releasing character surpassing that of alkyl phosphines and commonly used N‐heterocyclic carbenes. This is demonstrated by their very small Tolman electronic parameters (TEPs) as well as extremely low P−Se coupling constants. Cone angles and buried volumes attest to the high steric demand exerted by the (di)carboranyl phosphines. The dicarboranyl phosphine AuI complexes show superior catalytic performance in the hydroamination of alkynes compared to the monocarboranyl phosphine analogs. [ABSTRACT FROM AUTHOR]

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N, P Ligands, palladium, phosphino hydrazone, platinum, Sonogashira cross-coupling Keywords: N, P Ligands; palladium; phosphino hydrazone; platinum; Sonogashira cross-coupling EN N, P Ligands palladium phosphino hydrazone platinum Sonogashira cross-coupling 1 1 1 10/30/23 20231001 NES 231001 B The cover picture shows b the three different bonding modes (mono-, bi- and tridentate) of the modular ligand towards palladium(II) or platinum(II), illustrated with Winston who kindly served as model. Front Cover: Modular Synthesis of Phosphino Hydrazones and Their Use as Ligands in a Palladium-Catalysed Cu-Free Sonogashira Cross-Coupling Reaction (ChemPlusChem 10/2023). [Extracted from the article]

Keywords: Carboranes; Homogeneous Catalysis; Ligand Design; Phosphines; Strong Donors; Transition Metal Complexes EN Carboranes Homogeneous Catalysis Ligand Design Phosphines Strong Donors Transition Metal Complexes 1 1 1 03/23/23 20230327 NES 230327 B Carboranes b . Frontispiece: On the Edge of the Known: Extremely Electron-Rich (Di)Carboranyl Phosphines Carboranes, Homogeneous Catalysis, Ligand Design, Phosphines, Strong Donors, Transition Metal Complexes. [Extracted from the article]

B9-functionalized carboranylphosphines with bulky electron-donating substituents display an extremely electron-releasing character, as reported by Evamarie Hey-Hawkins et al. in their Research Article (e202218648). The compounds exert a high steric demand, which allows the mesityl derivatives to form stabilized phosphoniumyl radical cations. Keywords: Carborane; Homogene Katalyse; Ligandendesign; Phosphane; Übergangsmetallkomplexe DE Carborane Homogene Katalyse Ligandendesign Phosphane Übergangsmetallkomplexe 1 1 1 03/23/23 20230327 NES 230327 B Carboranes b . [Extracted from the article]