Chemistry of organosilicon compounds

We demonstrate a photochemical reaction between graphene and benzoyl peroxide. This reaction introduces spatially localized defects into the graphene basal plane. The reactivity of the single-layer graphene is ∼14 times higher than that of the double-layer graphene. Our result suggests that photoexcited graphene transfers a hot electron to benzoyl peroxide and induces its decomposition to a phenyl radical.

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Photochemical reactivity of graphene.

Using aryldiazonium salts that are air-stable and easily synthesized, we describe here a one-step, room-temperature route to direct covalent bonds between π-conjugated organic molecules on three material surfaces:  Si, GaAs, and Pd. The Si can be in the form of single crystal Si including heavily doped p-type Si, intrinsic Si, heavily doped n-type Si, on Si(111) and Si(100), and on n-type polycrystalline Si. The formation of the aryl−metal or aryl−semiconductor bond attachments was confirmed by corroborating evidence from ellipsometry, reflectance FTIR, XPS, cyclic voltammetry, and AFM analyses of the surface-grafted monolayers. A data-encompassing explanation for the mechanism suggests a diazonium activation by reduction at the open circuit potential, with aryl radical secondary products bonding to the surface. The synthetic details are included for preparing the surface-grafted monolayers and the precursor diazonium salts. This spontaneous diazonium activation reaction offers an attractive route to high...

Direct covalent grafting of conjugated molecules onto Si, GaAs, and Pd surfaces from aryldiazonium salts.

The de nouvo synthesis of small organic heterocyclic molecules has benefited from recent protocols for copper-facilitated additions of heteroatoms to alkenes, alkynes and arenes This tutorial review summarizes a number of these recent contributions Copper salts can facilitate bond formations due to their ability to serve as Lewis acids, oxidizing agents and transition metal catalysts The current understanding of the mechanisms of these reactions is presented This review should be of interest to chemists involved in the synthesis of heterocycles and those investigating transition metal facilitated reactions

http://aether.cmi.ua.ac.be/artikels/MB_12321.pdf

O. Simamura

Papers

Influence of substituent groups in the arylation of substituted benzenes by aryl radicals derived from p-substituted N-nitrosoacetanilides

Reduction of diazonium salts with silyl and stannyl hydrides

Decomposition of benzoyl peroxide in benzene in the presence of oxygen

The kinetics of the reactions of acyl peroxides with alkali iodides—I: The reactions of aroyl peroxides with potassium iodide

Decomposition of sodium peroxybenzoate in sodium hydroxide solution