The (cAAC)2Mn complex (cAAC=cyclic alkyl(amino)carbene) features a linear two‐coordinate Mn center. The antiferromagnetic coupling of a radical electron, delocalized on two carbene C atoms, with the central MnI having d6 electronic configuration, mainly contributes to the ST=3/2 ground state. Treatment of (cAAC)2Mn with H2 at RT resulted in the addition of H atoms at both “carbene” C atoms, leaving the central Mn atom in the ST=5/2 spin ground state.

Irradiation of rhodium(II) azido complex [Rh(N3){N(CHCHPtBu2)2}] allowed for the spectroscopic characterization of the first reported rhodium complex with a terminal nitrido ligand. DFT computations reveal that the unpaired electron of rhodium(IV) nitride complex [Rh(N){N(CHCHPtBu2)2}] is located in an antibonding Rh-N π* bond involving the nitrido moiety, thus resulting in predominant N-radical character, in turn providing a rationale for its transient nature and observed nitride coupling to dinitrogen.

Sequential twofold meta-C–H/ortho-C–H functionalization was achieved by means of versatile ruthenium­(II) biscarboxylate catalysis. The double C–H activation proved viable in a one-pot fashion with the assistance of synthetically useful imidates. The operationally simple twofold C–H functionalization occurred with high levels of positional selectivity control and was conducted in a nonsequential manner by the judicious choice of the reaction temperature. Detailed experimental mechanistic studies, including unprecedented electron paramagnetic resonance (EPR) experiments, provided strong support for homolytic C–X bond cleavage and facile C–H ruthenation, while a computational density functional theory (DFT) analysis was supportive of a novel mechanistic scenario involving synergistic catalysis via cyclometalated ruthenium­(III) complexes as key intermediates.

A radical change: Cyclic alkyl(amino) carbenes formed zwitterionic adducts with SiCl4, which were further converted into carbon‐centered stable radicals by changing the donor‐acceptor C→Si coordinate bond into a CSi covalent bond through a KC8 reduction. As the carbon radical site was directly bonded to a SiCl3 unit, a radical center that is right next to an acceptor has been generated.

Two (cAAC)2Cu complexes, featuring a two-coordinate copper atom in the formal oxidation state zero, were prepared by reducing (Et2-cAAC)2Cu(+)I(-) with metallic sodium in THF, and by a one-pot synthesis using Me2-cAAC, Cu(II)Cl2, and KC8 in toluene in a molar ratio of 2:1:2, respectively. Both complexes are highly air and moisture sensitive but can be stored in the solid state for a month at room temperature. DFT calculations showed that in these complexes the copper center has a d(10) electronic configuration and the unpaired electron is delocalized over two carbene carbon atoms. This was further confirmed by the EPR spectra, which exhibit multiple hyperfine lines due to the coupling of the unpaired electron with (63,65)Cu isotopes, (14)N, and (1)H nuclei.