Ruthenium-Ruthenium-Bonded [Bis{corrolato-ruthenium(III)}] (n=0, +1, -1) Complexes: Model Compounds for the Photosynthetic Special Pair.

We present herein the synthesis of three new bis(corrolato-ruthenium(III)) complexes containing unsupported Ru-Ru bonds and their characterization in different redox states. The H NMR spectra of the bis(corrolato-ruthenium(III)) complexes displayed "normal" chemical shifts and the compounds proved to be EPR-silent. Crystallographic characterization of the dimers indicated Ru-Ru distances of 2.

Phosphinines versus mesoionic carbenes: a comparison of structurally related ligands in Au(i)-catalysis.

Gold(i) complexes based on a 2,4,6-triarylphosphinine and a mesoionic carbene derivative have been prepared and characterized crystallographically. Although structurally related, both heterocycles differ significantly in their donor/acceptor properties. These opposed electronic characteristics have been exploited in Au(i)-catalyzed cycloisomerization reactions.

Palladium(ii)-Acetylacetonato Complexes with Mesoionic Carbenes: Synthesis, Structures and Their Application in the Suzuki-Miyaura Cross Coupling Reaction.

A series of novel palladium(ii) acetylacetonato complexes bearing mesoionic carbenes (MICs) have been synthesized and characterized. The synthesis of the complexes of type (MIC)Pd(acac)I (MIC = 1-mesityl-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene (), 1,4-(2,4,6-methyl)-phenyl-3-methyl-1,2,3-triazol-5-ylidene (), 1,4-(2,6-diisopropyl)-phenyl-3-methyl-1,2,3-triazol-5-ylidene (); acac = acetylacetonato) via direct metalation starting from the corresponding triazolium iodides and palladium(ii) acetylacetonate is described herein. All complexes were characterized by ¹H- and C-NMR spectroscopy and high resolution mass spectrometry.

Heteromultimetallic Complexes with Redox-Active Mesoionic Carbenes: Control of Donor Properties and Redox-Induced Catalysis.

Mesoionic carbenes (MICs) are currently hugely popular as ligands, and triazolylidenes are arguably the most prominent classes of such MICs. Mesoionic carbenes with ferrocenyl substituents are presented that can act as metalloligands for the generation of heteromultimetallic iridium(I) and gold(I) complexes. The ferrocenyl substituents allow for reversible oxidation of these heteromultimetallic complexes, and these oxidation steps have a strong influence on the donor properties of the MICs.

Heterobimetallic complexes with redox-active mesoionic carbenes as metalloligands: electrochemical properties, electronic structures and catalysis.

A mesoionic carbene with a ferrocene backbone is used as a metalloligand to generate the first example of their Fe-Au heterobimetallic complexes. The details of geometric and electronic structures in different redox states and preliminary catalytic results are presented.

Cooperative catalysis: electron-rich Fe-H complexes and DMAP, a successful "joint venture" for ultrafast hydrogen production.

A series of defined iron-hydrogen complexes was prepared in a straightforward one-pot approach. The structure and electronic properties of such complexes were investigated by means of quantum-chemical analysis. These new complexes were then applied in the dehydrogenative silylation of methanol.