Aryl rearrangements triggered by Cl extraction from starting from trans-[AuIII(Rf)2Cl2]– (Rf = C6F3Cl2-3,5), led fastly to a mixture of [Au(Rf)3(solv)], [Au(Rf)2Cl(solv)], and [Au(Rf)Cl2(solv)] (solv = OEt2, OH2). 19F NMR and...

Analysis of the bonding contributions in molecules [M III Cp*(L)XY] (M = Rh, Ir; Cp* = C 5 Me 5 ; L = CO, CN − , CNR) has uncovered a rich variety of types of interaction that seem to have escaped detection so far, in spite of the continuous popularity of cyclopentadienyl transition-metal complexes since the 1970s. At variance with the MCO bond in square-planar systems, which shows typical metal-to-CO π-back-donation, the nonorthogonal arrangement of the Cp* plane and RhCO fragment and the pseudooctahedral geometry lead to the observation of many direct lateral donations from other ligands that do not involve the metal orbitals, and we name side donations, for instance, Cp* → π*(CO), Cl → π*(CO), and F → π*(CO). Hybrid donations partially involving the metal, M−C aryl → π*(CO), are also observed. The summation of multiple contributions other than back-donation can easily account for about 20% of the electron donation to the π*(CO) orbitals.

Mechanistic proposals for the C-H activation reaction enabled by mono-N-protected amino acid ligands (MPAAs) have been supported by DFT calculations. The direct experimental observation of the ligand-assisted C-H activation has...

19F NMR monitoring shows that heating trans-[AuIIIRf2I2]‒ solutions (Rf = C6F3Cl2-3,5) leads to formation of cis-[AuRf2I2]‒, [AuRf3I]‒ and [AuRfI3]‒ via kinetic competition between isomerization and Rf/I scrambling. The system evolution...

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