An extremely electron poor Au(III) trication bearing acetonitrile ligands.

The synthesis and structural characterization of an electron poor Au(III) trication bearing 2 imidazole and 2 acetonitrile ligands is described. The new complex is capable of aryl C-H metalation with the formation of a monomesitylene complex and also demonstrated to be highly oxidizing in the rapid room temperature conversion of cyclohexene to benzene.

Electrophilic activation of molecular bromine mediated by I(III).

In pursuit of a genuine bromo-λ-iodane, it has been found that the combination of Br and electron deficient λ-iodanes can result in the delivery of both bromine atoms from Br to a range of aryl substrates, some highly deactivated. These brominations occur rapidly in common chlorinated solvents at room temperature and can be achieved with the catalytic activation of commercially available PhI(OAc) and PhI(OTFA). -NO substituted derivatives are employed to direct bromination towards more deactivated substrates.

ArI(NTf): the boundary of oxidative capacity for ArIL?

Synthesis and crystallographic characterization of NO-CH-I(NTf) (NTf = bistriflimide) is reported. Experimental results find that this compound can perform oxidation reactions that ArI(OTf) is unable to and theoretical analysis indicates Ar-I(NTf) is the most oxidizing in the ArIL class of compounds known and may also be the most oxidizing compound in the class practically possible.

C-H, Si-H and C-F abstraction with an extremely electron poor I(III) reagent.

The recently discovered I(III) reagent NO-CH-I(OTf) is found to rapidly react with hydride sources, including HSiEt and relatively hydridic C-H precursors. These represent the first distinct reactions involving direct hydride abstraction by I(III) under ambient conditions. Direct C-F abstraction is also demonstrated, as well as oxidation of cyclic alkenes to aromatic rings, all representing new reactions for I(III) demonstrating the very high reactivity of NO-CH-I(OTf).

Structural verification and new reactivity for Stang's reagent, [PhI(CN)][OTf].

The structure of Stang's reagent [PhI(CN)][OTf] is confirmed by X-ray crystallography and is determined to be best described as an ion-pair in organic solution. It is found to be a strong Lewis acid, but reaction with pyridine ligands gives [Pyr-CN][OTf] salts oxidation of pyridine giving a new derivative of the CDAP reagent widely used as an activation agent for polysaccharides.

An International Study Evaluating Elemental Analysis.

Based on statistical analysis of CHN combustion results of 18 international service providers, it is determined that the ±0.4% deviation most commonly required by chemistry journals is not justified.

PhICl is activated by chloride ions.

A study on the potential activating role of pyridine in the electrophilic chlorination of anisole by PhICl2 has led to the discovery that soluble sources of chloride ions activate PhICl2 in the reaction at catalytic loadings, greatly increasing the rate of chlorination. It is further shown that presence of chloride increases the rate of decomposition of PhICl2 into PhI and Cl2. The specific mechanism by which chloride induces electrophilic chlorination and decomposition of PhICl2 remains an open question.