Application of Electron-Withdrawing Coordinatively Unsaturated η⁶-Arene β-Diketiminato–Ruthenium Complexes in Lewis Acid Catalyzed Diels–Alder Reactions

Tuning steric and electronic effects in transition-metal β-diketiminate complexes

“…46 Ruthenium(II) complexes of L CF3, m -CF3 Ru(Cl)(Ar) (Ar = arene ligand) were studied to determine the electronic effects of the supporting ligand on the metal and the other coordinating ligands in comparison to analogous complexes with the L Me, m -Me supporting ligand. 85 Interestingly, there was no clear trend between the Ru II /Ru III redox potentials from the cyclic voltammograms through the series L Me,Me , L Me, m -Me , L CF3, m -Me , and L CF3, m -CF3 , indicating that other factors also play a role. 86 …”

“…For example, the chemical shift of the backbone (α-C) proton shifted downfield when CF 3 was substituted for CH 3 on backbone and for meta - positions on the N -aryl. 85 This is correlated to the deshielding effect with more electron withdrawing groups attached directly to the π system.…”

Catalytic sugar-assisted transfer hydrogenation with Ru(II), Rh(III) and Ir(III) halfsandwich complexes

“…Such compounds with chelating nitrogen ligands are effectively used in catalysis, e. g. in water oxidation [23], intramolecular hydroamination of alkynes [24], Diels-Alder reactions [25], asymmetric Michael addition reactions [26], asymmetric hydrogenation [27,28], and transfer hydrogenation [29][30][31], reactions of ketones and imines.…”

“…The formerly unknown precursor complexes with methyl 2,3-diamino-4,6-O-benzylidene-2,3-dideoxy-␣-D-hexopyranosides (compounds 1-4, Chart 1), methyl 2-amino-4,6-OChart 1. Diaminomonosaccharides 1-4, methyl 2-amino-4,6-O-benzylidene-2,3-dideoxy-3-tosylamido-␣-D-glucopyranoside (5) and corresponding diamino derivatives (S)-2,2 -diamino-1,1 -binaphthalene (6) and (R,R)-1,2-diphenylethylenediamine (7) and their halfsandwich complexes of iridium(III), -rhodium(III) and ruthenium(II) (8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25) for transfer hydrogenation ([T-4-R] and [T-4-S] denote the absolute configuration of the metal center in a pseudo-tetrahedral environment following the CIP rules).…”

Micellar promoted alkenes isomerization in water mediated by a cationic half-sandwich Ru(II) complex

“…Examples span from the allylic substitution reaction [19], to the Diels-Alder cycloaddition reaction with high selectivity towards the exo product [20], to the [2 + 2 + 2] cyclotrimerization of alkynes leading to aromatic compounds [21] and to the cyclopropanation of alkenes with diazoacetate carbene precursors with good selectivity for the formation of the cis isomer [22], just to name a few. As long as intramolecular reactions are concerned, the Ru-catalyzed isomerization of alkenes has been known for decades [23] including some recent examples based on monocationic Ru(II) species bearing 1-phenyl-indenyl and chloride anionic ligands [24].…”