Redox-Switchable Behavior of Transition-Metal Complexes Supported by Amino-Decorated N-Heterocyclic Carbenes.

The coordination chemistry of the N-heterocyclic carbene ligand IMes(NMe2)2, derived from the well-known IMes ligand by substitution of the carbenic heterocycle with two dimethylamino groups, was investigated with d6 [Mn(I), Fe(II)], d8 [Rh(I)], and d10 [Cu(I)] transition-metal centers. The redox behavior of the resulting organometallic complexes was studied through a combined experimental/theoretical study, involving electrochemistry, EPR spectroscopy, and DFT calculations. While the complexes [CuCl(IMes(NMe2)2)], [RhCl(COD)(IMes(NMe2)2)], and [FeCp(CO)2 (IMes(NMe2)2)](BF4) exhibit two oxidation waves, the first oxidation wave is fully reversible but only for the first complex the second oxidation wave is reversible. The mono-oxidation event for these complexes occurs on the NHC ligand, with a spin density mainly located on the diaminoethylene NHC-backbone, and has a dramatic effect on the donating properties of the NHC ligand. Conversely, as the Mn(I) center in the complex [MnCp(CO)2 ((IMes(NMe2)2)] is easily oxidizable, the latter complex is first oxidized on the metal center to form the corresponding cationic Mn(II) complex, and the NHC ligand is oxidized in a second reversible oxidation wave.

Ni and Pd N-confused porphyrin complexes as catalysts for the synthesis of cyclic carbonates from epoxides and CO2.

We have demonstrated the design of a novel bifunctional catalyst that is based on an N-confused tetraphenylporphyrin (NCTPP) motif for the cycloaddition of an epoxide to carbon dioxide via cooperative activation of the epoxide through a Pd(ii) or Ni(ii) metal center and a peripheral benzoate moiety with percent conversions of up to 99% and TON = 7000.

Unveiling the redox-active character of imidazolin-2-thiones derived from amino-substituted N-heterocyclic carbenes.

IMes-derived thioureas in which the imidazolyl ring is directly substituted by one or two dimethylamino groups are redox-active, exhibiting one and two oxidized states, respectively. The structure, stability, and electronics of the oxidized species are investigated, emphasizing the decisive role of the amino substituents.

Ruthenium Catalysts Supported by Amino-Substituted N-Heterocyclic Carbene Ligands for Olefin Metathesis of Challenging Substrates.

N-Heterocyclic carbene (NHC) ligands IMesNMe2 and IMes(NMe2)2 derived from the well-known IMes ligand by substituting the carbenic heterocycle with one and two dimethylamino groups, respectively, were employed for the synthesis of second-generation Grubbs- and Grubbs-Hoveyda-type ruthenium metathesis precatalysts. Whereas the stability of the complexes was found to depend on the degree of dimethylamino-substitution and on the type of complex, the backbone-substitution was shown to have a positive impact on their catalytic activity in ring-closing metathesis, with a more pronounced effect in the second-generation Grubbs-type series. The new complexes were successfully implemented in a number of challenging olefin metathesis reactions leading to the formation of tetra-substituted C=C double bonds and/or functionalized compounds.