0000000000385846
AUTHOR
Julio Esteban
Kinetico-mechanistic studies of the acidolysis of Rh-C bonds in monocyclometallated dirhodium(II) acetato complexes; influence of electronic and steric effects.
The protonation/demetallation reaction, in CD(3)COOD, of phosphine monometallated triacetato-bridged dirhodium(ii) complexes of general formulae [Rh(2)(μ-OOCCH(3))(3){(RC(5)CH(3))P(RC(6)H(4))(2)}(2)] has been studied from a kinetico-mechanistic perspective. The process has been monitored via the disappearance of the nuclear magnetic resonance signals of the protons present in the non-metallated ortho positions of the phosphine ligand and taking advantage of the relatively fast back metallation process that follows the acidolysis reaction, the sequence behaving as an overall equilibrium reaction. The process has a high associative character with important entropy demands, increasing both for…
Analysis of the main structural trends for biscyclometalated dinuclear rhodium compounds of general formula Rh2(O2CR)2(PC)2·2H2O
Abstract A new series of biscyclometalated dinuclear rhodium (II) compounds with the general formula Rh2(O2CR)2(PC)2 · 2H2O, being PC = (C6H4)P(C6H5)2, R = CH3 (1 · 2H2O), PC = [(p-CH3 OC6H3)P(p-CH3 OC6H4)2], R = CF3 (2 · 2H2O), PC = (C6H4)P[CH(CH3)2]2, R = CH3 (3 · 2H2O) and PC = (C6H4)P(C6H5)2, R = C6F5 (4 · 2H2O) has been obtained. The crystal structures for these compounds have been determined by X-ray diffraction and the main structural trends, bond lengths, bond angles and torsion angles have been analyzed, and have also been compared with the structural parameters for different analogous complexes described previously in the literature.
Determination of equilibrium constants and computational interaction energies for adducts of [Rh2(RCO2)(4-n)(PC)n] (n = 0-2) with Lewis bases.
Properties of dirhodium catalysts with cyclometalated aryl phosphine ligands have been studied. We report here the study of the acid−base reaction of Rh2(RCO2)2(PC)2(H2O)2 catalysts (PC = cyclometalated aryl phosphine) with different Lewis bases. The determination of the equilibrium constants of these reactions can be used to study to which extent the properties of the axial coordination site of the catalyst, considered the active site, are affected by modification of the metalated phosphines, the carboxylate ligands, or the incoming axial ligand. The trends in the computational density functional theory interaction energies show good agreement with the major trends in the equilibrium const…
Analysis of the main structural trends for biscyclometalated dinuclear rhodium compounds with nitrogen donor axial ligands
A new series of biscyclometalated dinuclear rhodium(II) compounds with the general formula Rh 2 (O 2 CR) 2 (PC) 2 · (N) 2 have been obtained, where PC is a cyclometalated phosphine, R an aliphatic group, and N a nitrogen donor ligand. The crystal structures for these compounds have been determined by X-ray diffraction. The most important structural trends have been analyzed, and have also been compared with the same parameters for different analogous compounds described previously in the literature.