Matches in SemOpenAlex for { <https://semopenalex.org/work/W1970085810> ?p ?o ?g. }
- W1970085810 endingPage "6971" @default.
- W1970085810 startingPage "6959" @default.
- W1970085810 abstract "A family of seven cationic gold complexes that contain both an alkyl substituted π-allene ligand and an electron-rich, sterically hindered supporting ligand was isolated in >90% yield and characterized by spectroscopy and, in three cases, by X-ray crystallography. Solution-phase and solid-state analysis of these complexes established preferential binding of gold to the less substituted C=C bond of the allene and to the allene π face trans to the substituent on the uncomplexed allenyl C=C bond. Kinetic analysis of intermolecular allene exchange established two-term rate laws of the form rate=k(1)[complex]+k(2)[complex][allene] consistent with allene-independent and allene-dependent exchange pathways with energy barriers of ΔG(≠)(1)=17.4-18.8 and ΔG(≠)(2)=15.2-17.6 kcal mol(-1), respectively. Variable temperature (VT) NMR analysis revealed fluxional behavior consistent with facile (ΔG(≠)=8.9-11.4 kcal mol(-1)) intramolecular exchange of the allene π faces through η(1)-allene transition states and/or intermediates that retain a staggered arrangement of the allene substituents. VT NMR/spin saturation transfer analysis of [{P(tBu)(2)o-binaphthyl}Au(η(2)-4,5-nonadiene)](+)SbF(6)(-) (5), which contains elements of chirality in both the phosphine and allene ligands, revealed no epimerization of the allene ligand below the threshold for intermolecular allene exchange (ΔG(≠)(298K)=17.4 kcal mol(-1)), which ruled out the participation of a η(1)-allylic cation species in the low-energy π-face exchange process for this complex." @default.
- W1970085810 created "2016-06-24" @default.
- W1970085810 creator A5003621928 @default.
- W1970085810 creator A5032223251 @default.
- W1970085810 creator A5042429033 @default.
- W1970085810 creator A5057234663 @default.
- W1970085810 date "2012-04-23" @default.
- W1970085810 modified "2023-10-18" @default.
- W1970085810 title "Structures and Dynamic Solution Behavior of Cationic, Two-Coordinate Gold(I)-π-Allene Complexes" @default.
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