Early transition metal complexes for direct C H bond functionalization of heteroatom-containing organic compounds

Valence-to-core X-ray emission spectroscopy of transition metal tetrahalides: mechanisms governing intensities

“…4) with all Kb 2,5 peak maxima aligned at 0 eV. where S mn ¼ w m w n are overlap integrals between the GTO basis functions that are gathered in the overlap matrix S. The matrices in eqn (5) have been extracted from the ORCA output files with the aid of the orca_2json program. With matrix C at hand, the contribution of a given atomic orbital j p to molecular orbital f i is quantified by taking the square of the corresponding matrix element c ip .…”

“…By construction, this approach renders 4p contribution as main component because of a clear separation into 3p (occupied) and 4p (unoccupied) orbitals within the atomic calculations. In the following projection of the atomic orbitals onto the molecular orbitals (see eqn (5)), this partitioning is maintained, leaving only 4p contribution to significantly modulate the intensity of the VtC peaks.…”

“…Transition metals play key structural and functional roles in biological processes, [1][2][3][4] catalytic transformations, 5 as well as in environmental 6 and material science. 7 Understanding the geometric and electronic structure changes that occur at transition metals during various processes is thus of broad general interest.…”

Synthesis, Characterization, and Reactivity of a Highly Oxidative Mononuclear Manganese(IV)–Bis(Fluoro) Complex

“…The activation of inert C–H bonds has been a challenging reaction for the functionalization of organic compounds in many chemical and pharmaceutical industries. − In the biological system, high-valent metal–(hydr)­oxo species have been invoked in a variety of metalloenzymes as a remarkable class of intermediates that cleave and functionalize strong C–H bonds through a hydrogen atom transfer (HAT) mechanism. − To date, through synthetic model chemistry, the mechanism of the C–H bond activation by metal oxido complexes has actively been discussed with regard to driving forces of the HAT between the C–H bond being cleaved and the O–H bond being formed. − The paradigm of thermodynamics on bond dissociation free energies (BDFEs) renders multiple mechanisms for the HAT involving (synchronous or asynchronous) proton-coupled electron transfer (PCET), and stepwise proton–electron transfer (PT/ET), or electron–proton transfer (ET/PT). These studies have expanded our understanding of the behavior of various catalysts involved in the C–H bond functionalization.…”

Synthesis of [2.2]Paracyclophane-Fused Heterocycles via Palladium-Catalyzed C–H Activation/Annulation of [2.2]Paracyclophanecarboxamides with Arynes

“…Product derivatizations were then carried out to showcase the utility of this reaction. The removal of the OMe group in ( S p )- 3a by NaH afforded the N–H product ( S p )- 4a almost in quantitative yield (Scheme b), and its structurally similar molecule is a N , O -chelating ligand in the hydroaminoalkylation reaction . UV–vis absorption spectra revealed that compound 4a can absorb light at 365 nm in CH 2 Cl 2 (Scheme S5), and it was further found that under blacklight-irradiation, 4a can act as an effective photocatalyst to realize the reductive cleavage of sulfonamides of the tosyl amide substrate 7 toward N -benzylbenzamide 8 (Scheme f) .…”