Oxy-functionalization of nucleophilic rhenium(I) metal carbon bonds catalyzed by selenium(IV)

We report that SeO_2 catalyzes the facile oxy-functionalization of (CO)_5Re(I)-Me^(δ−) with IO_4− to generate methanol. Mechanistic studies and DFT calculations reveal that catalysis involves methyl group transfer from Re to the electrophilic Se center followed by oxidation and subsequent reductive functionalization of the resulting CH_3Se(VI) species. Furthermore, (CO)_3Re(I)(Bpy)-R (R = ethyl, n-propyl, and aryl) complexes show analogous transfer to SeO_2 to generate the primary alcohols. This represents a new strategy for the oxy-functionalization of M−R^(δ−) polarized bonds

Chemical functionalization of graphene

Experimental and theoretical results on chemical functionalization of graphene are reviewed. Using hydrogenated graphene as a model system, general principles of the chemical functionalization are formulated and discussed. It is shown that, as a rule, 100% coverage of graphene by complex functional groups (in contrast with hydrogen and fluorine) is unreachable. A possible destruction of graphene nanoribbons by fluorine is considered. The functionalization of infinite graphene and graphene nanoribbons by oxygen and by hydrofluoric acid is simulated step by step.Comment: 13 pages, 11 figures. Invited paper for J. Phys. Cond. Mater. "Graphene" special issue. References added, typos correcte

A solvent-free Diels-Alder reaction of graphite into functionalized graphene nanosheets

A solvent-free Diels-Alder reaction was carried out by heating a mixture of graphite and a typical dienophile, maleic anhydride (MA) or maleimide (MI), in a sealed glass ampoule of argon. The functionalization of graphite with dienophiles was confirmed by various characterization techniques, suggesting the efficient functionalization and delamination of graphite into a few layers of graphitic nanosheets.close0

Regio-selective substitution at the 1,3- and 6,8-positions of pyrene for the construction of small dipolar molecules

© 2015 American Chemical Society. This article presents a novel asymmetrical functionalization strategy for the construction of dipolar molecules via efficient regioselective functionalization along the Z-axis of pyrene at both the 1,3- and 6,8-positions. Three asymmetrical ly substituted 1,3-diphenyl-6,8-R-disubsituted pyrenes were fully characterized by X-ray crystallography, photophysical properties, electrochemistry, and density functional theory calculations

Synthesis and late-stage functionalization of complex molecules through C-H fluorination and nucleophilic aromatic substitution.

We report the late-stage functionalization of multisubstituted pyridines and diazines at the position α to nitrogen. By this process, a series of functional groups and substituents bound to the ring through nitrogen, oxygen, sulfur, or carbon are installed. This functionalization is accomplished by a combination of fluorination and nucleophilic aromatic substitution of the installed fluoride. A diverse array of functionalities can be installed because of the mild reaction conditions revealed for nucleophilic aromatic substitutions (S(N)Ar) of the 2-fluoroheteroarenes. An evaluation of the rates for substitution versus the rates for competitive processes provides a framework for planning this functionalization sequence. This process is illustrated by the modification of a series of medicinally important compounds, as well as the increase in efficiency of synthesis of several existing pharmaceuticals

The functionalization of carbon nanotubes using a batch oscillatory flow reactor

This paper describes an efficient method for the functionalizing of multi-walled carbon nanotubes (MWCNT) using oscillatory flow mixing (OFM). A 3. l batch oscillatory flow reactor (OFR) was designed and constructed for pilot scale functionalization of MWCNT in order to potentially improve their compatibility within a thermoplastic polyphenylene sulphide (PPS) matrix. The OFM batch reactor consisted of a jacketed cylindrical vessel with a vertical axial oscillator that contained a series of baffled mixing plates. MWCNTs dispersed in dimethylformamide (DMF) were introduced into the reactor and a two stage reaction for functionalizing MWCNTs with PPS compatible groups was carried out under oscillation of baffles at elevated temperatures. Fluid mixing observations in the reactor showed that MWCNTs formed a uniform dispersion of aggregated flocs before and during the functionalization reaction. On completion of the reaction and cessation of the oscillation, the aggregated flocs of MWCNT rapidly sedimented at the bottom of the reactor; hence could be collected as a concentrated mass thereby facilitating the separation of functionalized MWCNTs from the solvent. The functionalized MWCNTs were dried and then characterized by transmission electron microscopy, infrared spectroscopy as well as thermal gravimetric analysis in order to investigate the extent of MWCNT functionalization. The characterization results confirmed the effective and relatively uniform functionalization of the MWCNTs despite formation of aggregates, indicating that OFM provides a viable approach for functionalizing MWCNTs