RESUMEN

Creation of confined coordination spaces with controlled flexibility is of importance in mimicking enzymatic reactions. We found that a simple, non-chelating 1,3-bis(diphenylphosphino)benzene (DPPBz) assembled two Cp*Ru units to give a dinuclear complex, wherein only one DPPBz supports an open framework without metal-metal bonding. Subsequent treatment with an excess of hydrazine resulted in formal 2e-/2H+ transfer from hydrazine to afford a diazene-bridged complex featuring intramolecular NHCl hydrogen bonds. In constrast, a monophosphine failed to stabilize the diazene-bridged dinuclear structure due to the lack of the enforcement of the conformation.

RESUMEN

Partial dehydrobromination of a diprotic pincer-type ruthenium complex in the presence of a rigid 1,3-bis(diphenylphosphino)benzene linker provided a dinuclear cage containing a guest template KBr surrounded by hydrogen bonds and electrostatic interactions. Dinitrogen and carbon disulfide were encapsulated into the cage with proton channels formed by the pyrazole arms in the pincer ligands.

RESUMEN

NNN and NCN pincer-type ruthenium(II) complexes featuring two protic pyrazol-3-yl arms with a trifluoromethyl (CF3 ) group at the 5-position were synthesized and structurally characterized to evaluate the impact of the substitution on the properties and catalysis. The increased Brønsted acidity by the highly electron-withdrawing CF3 pendants was demonstrated by protonation-deprotonation experiments. By contrast, the IR spectra of the carbonyl derivatives as well as the cyclic voltammogram indicated that the electron density of the ruthenium atom is negligibly influenced by the CF3 group. Catalysis of these complexes in the decomposition of formic acid to dihydrogen and carbon dioxide was also examined. The NNN pincer-type complex 1 a with the CF3 group exhibited a higher catalytic activity than the tBu-substituted analogue 1 b. In addition, the bis(CF3 -pyrazolato) ammine derivative 4 catalyzed the reaction even in the absence of base additives.

Asunto(s)

RESUMEN

Evaluation of the acidity of proton-responsive ligands such as protic N-heterocyclic carbenes (NHCs) bearing an NH-wingtip provides a key to understanding the metal-ligand cooperation in enzymatic and artificial catalysis. Here, we design a CNN pincer-type ruthenium complex 2 bearing protic NHC and isoelectronic pyrazole units in a symmetrical skeleton, to compare their acidities and electron-donating abilities. The synthesis is achieved by direct C-H metalation of 2-(imidazol-1-yl)-6-(pyrazol-3-yl)pyridine with [RuCl2 (PPh3 )3 ]. 15 N-Labeling experiments confirm that deprotonation of 2 occurs first at the pyrazole side, indicating clearly that the protic pyrazole is more acidic than the NHC group. The electrochemical measurements as well as derivatization to carbonyl complexes demonstrate that the protic NHC is more electron-donating than pyrazole in both protonated and deprotonated forms.

RESUMEN

A reaction of a 2-(imidazol-1-yl)methyl-6-(pyrazol-3-yl)pyridine with [RuCl2 (PPh3 )3 ] resulted in tautomerization of the imidazole unit to afford the unsymmetrical pincer-type ruthenium complex 2 containing a protic pyrazole and N-heterocyclic carbene (NHC) arms. Deprotonation of 2 with one equivalent of a base led to the formation of the NHC-pyrazolato complex 3, indicating that the protic NHC arm is less acidic. When 2 was treated with two equivalents of a base under H2 or in 2-propanol, the hydrido complex 4 containing protic NHC and pyrazolato groups was obtained through metal-ligand cooperation.