ABSTRACT
Computational studies on decarboxylative C-H alkenylations provided key insights into the solvent-robust nature of C-H activation/decarboxylation domino reactions. These properties were exploited for ruthenium(II)-catalyzed C-H alkylations by a decarboxylative process with ample scope under copper-free and silver-free reaction conditions.
ABSTRACT
Ruthenium(II) bis(carboxylate)s proved highly effective for two decarboxylative C-H alkenylation strategies. The decarboxylation proceeded efficiently at rather low temperatures. The unique versatility of the decarboxylative ruthenium(II) catalysis is reflected in the oxidative olefinations with alkenes as well as the redox-neutral hydroarylations of alkynes.
ABSTRACT
Ruthenium(II) oxidase catalysis by direct dioxygen-coupled turnover enabled step-economical oxidative C-H alkenylation reactions at ambient pressure. Versatile ruthenium(II) biscarboxylate catalysts displayed ample substrate scope and proved applicable to weakly coordinating and removable directing groups. The twofold C-H functionalization strategy was characterized by exceedingly mild reaction conditions as well as excellent positional selectivity.
ABSTRACT
The aurophilicity exhibited by Au(I) complexes depends strongly on the nature of the supporting ligands present and the length of the Au-element (Au-E) bond may be used as a measure of the donor-acceptor properties of the coordinated ligands. A binuclear iron-gold complex, [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene-2κC(2)]dicarbonyl-1κ(2)C-(1η(5)-cyclopentadienyl)gold(I)iron(II)(Au-Fe) benzene trisolvate, [AuFe(C5H5)(C27H36N2)(CO)2]·3C6H6, was prepared by reaction of K[CpFe(CO)2] (Cp is cyclopentadienyl) with (NHC)AuCl [NHC = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]. In addition to the binuclear complex, the asymmetric unit contains three benzene solvent molecules. This is the first example of a two-coordinated Au atom bonded to an Fe and a C atom of an N-heterocyclic carbene.
