Acceleration of nucleophilic CH activation by strongly basic solvents.

(IPI)Ru(II)(OH)(n)(H(2)O)(m), 2, where IPI is the NNN-pincer ligand, 2,6-diimidizoylpyridine, is shown to catalyze H/D exchange between hydrocarbons and strongly basic solvents at higher rates than in the case of the solvent alone. Significantly, catalysis by 2 is accelerated rather than inhibited by increasing solvent basicity. The evidence is consistent with the reaction proceeding by base modulated nucleophilic CH activation.

Experimental realization of catalytic CH4 hydroxylation predicted for an iridium NNC pincer complex, demonstrating thermal, protic, and oxidant stability.

A discrete, air, protic, and thermally stable (NNC)Ir(III) pincer complex was synthesized that catalytically activates the CH bond of methane in trifluoroacetic acid; functionalization using NaIO4 and KIO3 gives the oxy-ester.

Facile functionalization of a metal carbon bond by O-atom transfer.

The facile conversion of M-R to M-OR that could be useful for the functionalization of electron-rich metal alkyl intermediates is shown to proceed via a Baeyer-Villiger-type pathway involving a nonredox, electrophilic, O-atom insertion in reactions with non-peroxo O-donors.

Carboxylic solvents and O-donor ligand effects on CH activation by Pt(II).

We report on the design of more efficient C-H activation catalysts based on DFT calculations. The first examples of well-defined, N,O-donor ligated platinum complexes that are competent for fast C-H activation are detailed. These complexes exhibit thermal and protic stability and are efficient catalysts for H/D exchange reactions with benzene.

CH activation with an O-donor iridium-methoxo complex.

A thermally and air stable O-donor, iridium-methoxo complex is reported that undergoes stoichiometric, intermolecular C-H activation of benzene with co-generation of methanol and the iridium-phenyl complex.

Variable solid state aggregations in a series of (isocyanide)gold(I) halides with the novel trimethylamine-isocyanoborane adduct.

This paper provides evidence that the degree of aurophilic character and resulting solid state arrangement observed in (isocyanide)gold(I) halides is in part dependent on the nature of halide substituent. In particular, we report here the synthesis of a series of novel (isocyanide)gold(I) halides involving trimethylamine-isocyanoborane, an unusual 'zwitterionic' isocyanide that is comparable to the more familiar methyl isocyanide, but potentially more strongly Lewis basic. The reaction of chloro(dimethyl sulfide)gold(I) and the isocyanoborane species, (RNC)(R =(H3C)3NB(H)2), gives the novel crystalline adduct [(RNC)AuCl] (1).