The hydroxylation of aromatic compounds by mononuclear nonheme iron(IV)-oxo complexes, [FeIV(Bn-tpen)(O)]2+ (Bn-tpen=N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine) and [FeIV(N4Py)(O)]2+ (N4Py=N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), has been investigated by a combined experimental and theoretical approach. In the experimental work, we have performed kinetic studies of t...

Displacements on benzenediazonium cation, C,jHsNz+, in solution in the absence of strong bases, reducing agents, or light proceed by rate-determining cleavage to a singlet phenyl cation intermediate, CsH5+, rather than by the bimolecular mechanism proposed in 1969. In aqueous solution at 2 5 O , only unrearranged products are obtained, and negligible incorporation of deuterium from solvent D2O ...

Preliminary validation of cyclopropene activation by an I(I)/I(III) catalysis manifold is disclosed to enable the direct tetrafluorination 3,3-diarylcyclopropenes. This transformation occurs through in situ generation ArI(III)F2, with inexpensive iodobenzene, amine·HF complexes and Selectfluor® serving as catalyst, fluoride source oxidant, respectively. Leveraging this approach, it has been pos...

Low-valent titanocene catalysts are a versatile tool for organic synthesis. They promote inter- and intramolecular reactions ranging from homolytic bond cleavages to reductive umpolung additions cyclizations in single electron steps. These heavily depend on the redox potential of an situ formed titanium(III) center, which can be adjusted by choice appropriate ligands. We herein review various c...