Generation and Structural Characterization of a Gold(III) Alkene Complex

Abstract

International audienceA Missing Gold Link: An Au(III) alkene complex has been prepared and characterized by NMR spectroscopy and X-ray crystallography. Its bonding features have been analyzed by DFT calculations and natural bond orbital (NBO) analysis. In [(cod)AuMe(2) ](+) , the unequal AuC bond lengths result from the domination of the preference of 1,5-cyclooctadiene (cod) for nonparallel double bonds over back donation from the metal which favors parallel double bonds

Cyclometalated Gold(III) Complexes: Synthesis, Reactivity, and Physicochemical Properties

“…[87] Upon treatment with trifluoromethanesulfonic acid (TfOH) at À78 8 8Ci nd ichloromethane,c omplex 96 was formed in 85 % yield. [87] Upon treatment with trifluoromethanesulfonic acid (TfOH) at À78 8 8Ci nd ichloromethane,c omplex 96 was formed in 85 % yield.…”

“…Compound 94 proved to be asuitable precursor for one of the few Au III diolefinic complexes reported to date. [87] Upon treatment with trifluoromethanesulfonic acid (TfOH) at À78 8 8Ci nd ichloromethane,c omplex 96 was formed in 85 % yield. Addition of 1,5-cyclooctadiene (cod) furnished Au IIIolefin complex 97 a,w hich could only be characterized by ad ownfield 1 HNMR shift of the cod vinylic protons (from d = 5.56 to 6.39 ppm).…”

Enhanced π‐Backdonation from Gold(I): Isolation of Original Carbonyl and Carbene Complexes

“…[2] Compared with other transition metals, the variety of gold complexes has long remained very limited. However, increasing efforts have been made over the past few years to isolate and characterize important classes of gold compounds such as p complexes, [3][4][5][6] vinyl complexes, [7] hydrides, [8] fluorides, [9] hydroxides and peroxides, [10] carbonyls, [11] and carbenoids. [12][13][14] Accordingly, our fundamental knowledge of gold organometallic chemistry has significantly progressed from both synthetic and bonding standpoints.…”

Cationic Gold(III) Alkyl Complexes: Generation, Trapping, and Insertion of Norbornene

“…[1] This elementary step has been extensively documented and thoroughly investigated with early to late transition metals, but strikingly it is unprecedented with gold.Over the last decade, our knowledge of gold(III) chemistry has tremendously progressed. A variety of highly reactive gold(III) complexes including p adducts of alkenes, [2,3] hydride, [4] hydroxide [5] /peroxide [6] /oxo, [7] and vinyl [8] /allenyl [9] species have been isolated as stable compounds. Important insights have also been gained in terms of reactivity.…”