The new complex [(η 6 -p-cym)RuCl(κ 2 -N,N-dmbpy)](BF 4 ) (pcym = p-cymene; dmbpy = 4,4′-dimethyl-2,2′-bipyridine) is water-soluble and active in the catalytic transfer hydrogenation (TH) of different ketones (cyclohexanone, 2-cyclohexenone, and 3-pentanone) to the corresponding alcohols using aqueous HCOONa/HCOOH as the hydrogen source at pH 4.4. A higher activity was found for the TH of the imine N-benzylideneaniline under the same conditions. Excellent results have been obtained for catalyst recycling. Aqua, formato, and hydrido species were detected by 1 H NMR experiments in D 2 O. Importantly, when the catalytic reaction was carried out in D 2 O, selective deuteration at the C α of the alcohols was observed due to a rapid Ru−H/D + exchange, which was also deduced theoretically. This process involves a reversal of polarity of the D + ion, which is transformed into a Ru−D function ("umpolung"). Negligible deuterium labeling was observed for the imine, possibly due to the high activity in the TH process and also to the decrease in the hydrido complex concentration due to the stability of a hydrido-imine intermediate. Both facts should ensure that the TH reaction will compete favorably with the Ru−H/D + exchange. The basic nature of the imine hydrogenation product can also hinder the stated Ru−H/D + exchange. On the basis of DFT calculations, all these hypotheses are discussed. In addition, calculations at this level also support the participation of the stated aqua, formato, and hydrido intermediates in the catalytic reaction and provide a detailed microscopic description of the full catalytic cycle. In the case of the imine TH process, the formation of the hydrido complex (decarboxylation step) is clearly the limiting step of the cycle. On the contrary, in the hydrogenation of cyclohexanone, both decarboxylation and reduction steps exhibit similar barriers, and due to the limitations of the solvent model employed, a definitive conclusion on the rate-determining step cannot be inferred.

Ruthenium derivatives of the type [RuCl(arene)(NN)][BPh 4 ] (arene = benzene, p-cymene) have been synthesized with NN = 2-hydroxyphenylbis(pyrazol-1-yl)methane (bpzmArOH) or 2-hydroxyphenylbis(3,5-dimethylpyrazol-1-yl)methane (bpz*mArOH). In the p-cymene derivative containing bpzmArOH, activation of the hydroxy group is observed and a scorpionate complex is obtained with the ligand behaving in a tridentate manner, [Ru(bpzmArO-κThe structure of this derivative and that of [RuCl(p-cymene)(bpz*mArOH)][BPh 4 ] were determined by X-ray diffraction. The new derivatives, along with other compounds previously described by us that contain similar ligands, were tested in the transfer hydrogenation of benzophenone and other carbonyl compounds under base-free conditions without any other additive to promote the reaction. The precursors were active in this process, and the p-cymene derivatives exhibited a higher activity than the benzene complexes. For the p-cymene complexes the activity was even higher than that found in the presence of base (KOH). The effect of the substituents on the methylene carbon was also studied. Mechanistic and kinetic studies were carried out, and hydride species were observed after a pretreatment of the precatalyst in 2-propanol. Taking into account all of the results, a proposal for the mechanism taking place during the hydrogenation of carbonyl groups under base-free conditions has been made.

The new ligands bis(pyrazol-1-yl)(pyridine-4yl)methane (bpzm4py) (L1) and bis(3,5-dimethylpyrazol-1yl)(pyridine-4-yl)methane (bpz*m4py) (L2) were synthesized and were made to react with different metallic starting materials. In the case of Pd(II), chloride or allyl trinuclear complexes were synthesized, in which the central palladium is bonded to two ligands through the pyridine moiety. Mononuclear [Pd(allyl)L]X complexes were also isolated. On using other M(II) centers (M = Co, Ni, Zn), which could adopt an octahedral geometry, box-like cyclic dimers formed by the self-assembly of two metal centers and two ligands in a head-to-tail disposition were obtained. All metal ions exhibited a distorted octahedral geometry. A complex of Ag(I) with similar cyclic dimers connected through difluorophosphate anions to generate zigzag chains was also crystallized. The silver center was five-coordinate and the chain interactions gave rise to the formation of sheets. In the solid state, different noncovalent interactions were present in the molecular and supramolecular structures, including hydrogen bonds, π−π stacking and anion−π or CH−π interactions. Examples of possible synergy between some of these interactions were found. Where possible, the solution chemistry was analyzed and correlated with the solid state structure. The existence of polynuclear species in solution was evaluated and the effect of some noncovalent interactions on the NMR resonances was observed.

Keywords: Ruthenium / Arene ligands / Homogeneous catalysis / Bis(pyrazolyl)methane / Transfer hydrogenation / X-ray structure determinationA new and safer methodology has been developed for the synthesis of bis(pyrazol-1-yl)methane ligands (NN). Several ligands containing different phenyl groups on the central carbon atom have been obtained. Ruthenium derivatives of the type [Ru(arene)Cl(NN)]BPh 4 (arene = benzene, p-cymene) have been synthesised using these ligands. One or two isomers that differ regarding the axial or equatorial disposition of the phenyl group on the metallacycle have been obtained. Their formation is rationalised by considering steric effects. The structures of five derivatives were determined by X-ray diffraction. In four complexes the phenyl substituent is in the axial disposition of the metallacycle and in one case in the equatorial orientation. The dihedral angle formed by the planes of the two pyrazole rings is always bigger for

The ortho-alkylation of phenols or aniline by catalytic C-H activation and multifunctional catalysis is described.