The reaction of a copper complex bearing iminosemiquinone ligands with a CF3(+) source provides an unprecedented Cu(II)-CF3 complex through ligand-based oxidation. Reactivity of this complex leads to nucleophilic trifluoromethylation of the ligand, suggesting an electronic interplay that results in a formal umpolung of the initial CF3(+).
A series of new secondary phosphine
oxide (SPO)–gold(I)
complexes have been synthesized and characterized by X-ray crystallography.
Complexes exhibited dimeric structures interconnected by O–H···Cl
hydrogen bonds. Their first use in homogeneous catalysis is reported
and suggests a broad field of application in prototypical enyne cycloisomerization
and hydroxy- and methoxycyclization reactions.
Tandem C-H activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox-active non-innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first-row transition metals have been shown to involve substrate-based aryl radicals, whereas our catalytic system likely involves ligand-centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner-sphere C-H activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble-metal-like behavior could be sustained by the redox-active non-innocent bisiminopyridine ligands.
The reaction is proposed to proceed through a metal‐based inner‐sphere C‐H activation involving concomitant electron transfer from the ligand and the substrate.
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