ChemInform Abstract: Carbon—Heteroatom Bond‐Forming Reductive Elimination from Palladium(IV) Complexes

Review: 78 refs.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/87067/1/201138215_ftp.pd

Pd-Catalyzed C–H Fluorination with Nucleophilic Fluoride

The palladium-catalyzed C–H fluorination of 8-methylquinoline derivatives with nucleophilic fluoride is reported. This transformation involves the use of AgF as the fluoride source in combination with a hypervalent iodine oxidant. Both the scope and mechanism of the reaction are discussed

Competition between sp³‑C–N vs sp³‑C–F Reductive Elimination from Pd^IV Complexes

This communication describes the design of a model system that allows direct investigation of competing sp³-C–N and sp³-C–F bond-forming reductive elimination from a Pd^IV fluoro sulfonamide complex. The reductive elimination selectivity varies dramatically as a function of reaction additives. A mechanism is proposed that provides a rationale for these effects

Phase Discrimination through Oxidant Selection in Low-Temperature Atomic Layer Deposition of Crystalline Iron Oxides

Control over the oxidation state and crystalline phase of thin-film iron oxides was achieved by low-temperature atomic layer deposition (ALD), utilizing a novel iron precursor, bis­(2,4-methylpentadienyl)­iron. This low-temperature (<i>T</i> = 120 °C) route to conformal deposition of crystalline Fe₃O₄ or α-Fe₂O₃ thin films is determined by the choice of oxygen source selected for the second surface half-reaction. The approach employs ozone to produce fully oxidized α-Fe₂O₃ or a milder oxidant, H₂O₂, to generate the Fe²⁺/Fe³⁺ spinel, Fe₃O₄. Both processes show self-limiting surface reactions and deposition rates of at least 0.6 Å/cycle, a significantly high growth rate at such mild conditions. We utilized this process to prepare conformal iron oxide thin films on a porous framework, for which α-Fe₂O₃ is active for photocatalytic water splitting

Phenyl Groups versus <i>tert</i>-Butyl Groups as Solubilizing Substituents for Some [5]Phenacenes and [7]Phenacenes

In recent years, we have used the photocyclizations of diarylethylenes to synthesize a number of [<i>n</i>]­phenacenes in the hope that they might be useful as the bridging groups for electron transfer processes in donor–bridge–acceptor molecules. Because [<i>n</i>]­phenacenes with <i>n</i> > 5 are very insoluble, their synthesis and characterization has required the attachment of solubilizing substituents such as <i>tert</i>-butyl. The studies of Pascal and co-workers of some large polynuclear aromatic compounds having multiple phenyl substituents prompted us to explore the use of phenyls as alternative solubilizing groups for [<i>n</i>]­phenacenes. Although phenyl groups turned out to provide significantly less solubilization than <i>tert</i>-butyl groups in these compounds, we found some interesting structural comparisons of the phenyl-substituted and <i>tert</i>-butyl-substituted [<i>n</i>]­phenacenes

Phenyl Groups versus <i>tert</i>-Butyl Groups as Solubilizing Substituents for Some [5]Phenacenes and [7]Phenacenes

In recent years, we have used the photocyclizations of diarylethylenes to synthesize a number of [<i>n</i>]­phenacenes in the hope that they might be useful as the bridging groups for electron transfer processes in donor–bridge–acceptor molecules. Because [<i>n</i>]­phenacenes with <i>n</i> > 5 are very insoluble, their synthesis and characterization has required the attachment of solubilizing substituents such as <i>tert</i>-butyl. The studies of Pascal and co-workers of some large polynuclear aromatic compounds having multiple phenyl substituents prompted us to explore the use of phenyls as alternative solubilizing groups for [<i>n</i>]­phenacenes. Although phenyl groups turned out to provide significantly less solubilization than <i>tert</i>-butyl groups in these compounds, we found some interesting structural comparisons of the phenyl-substituted and <i>tert</i>-butyl-substituted [<i>n</i>]­phenacenes