Alkyl abstraction from {Me3SiN(CH2CH2NSiMe3)2}ZrR2 (N3ZrR2; R = CH2Ph, Me) using B(C6F5)3 affords cationic alkyl complexes stabilized by a diamide ligand. The ionic η2-benzyl adduct decomposes slowly to give a cationic cyclometalation product, which coordinates the [PhCH2B(C6F5)3]- anion; the methyl cation coordinates the anion [MeB(C6F5)3]- via a Zr···Me−B interaction. The complexes exhibit moderate ethene polymerization activity.

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Monomeric CuII sites supported on alumina, prepared using surface organometallic chemistry, convert CH4 to CH3OH selectively. This reaction takes place by formation of CH3O surface species with the concomitant reduction of two monomeric CuII sites to CuI, according to mass balance analysis, infrared, solid‐state nuclear magnetic resonance, X‐ray absorption, and electron paramagnetic resonance spectroscopy studies. This material contains a significant fraction of Cu active sites (22 %) and displays a selectivity for CH3OH exceeding 83 %, based on the number of electrons involved in the transformation. These alumina‐supported CuII sites reveal that C−H bond activation, along with the formation of CH3O‐ surface species, can occur on pairs of proximal monomeric CuII sites in a short reaction time.

β-Me elimination from cationic neopentyl complexes, [Cp‘2Zr(CH2CMe3)]+, has been demonstrated. The more crowded complex (Cp‘ = C5Me5) eliminates isobutene instantaneously at −75 °C, whereas the less crowded analogue (Cp‘ = C5H5) is stable in solution at 0 °C but undegoes reversible β-Me elimination at 25 °C; strong anion or Lewis base coordination suppresses β-Me elimination, consistent with involvement of a 14-electron species.

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