Synthesis, characterization and investigations on the reactivity of the novel metal basic, yet isolable 14 VE NHC-complexes [M(iPrIm)] (M = Pd , Pt ; iPrIm = 1,3-di-isopropyl-imidazolin-2-ylidene; VE = valence electron; NHC = N-heterocyclic carbene) is reported and compared to the chemistry of the corresponding nickel complex. Quantum chemical analyses reveal that differences in the reactivity of group 10 NHC complexes are caused by differences in the rigidity and thus activation strain associated with bending the corresponding d-[M(NHC)] fragments during reaction. These results should have implications for the understanding of the fundamental steps in catalytic cycles, in which such complex fragments are employed.
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Bite-angle bending as a key for understanding group-10 metal reactivity of d-[M(NHC)] complexes with sterically modest NHC ligands.
Chem Sci
February 2015
Institut für Anorganische Chemie , Julius-Maximilians-Universität Würzburg, Am Hubland , D-97074 Würzburg , Germany . Email:
Synthesis, characterization and investigations on the reactivity of the novel metal basic, yet isolable 14 VE NHC-complexes [M(iPrIm)] (M = Pd , Pt ; iPrIm = 1,3-di-isopropyl-imidazolin-2-ylidene; VE = valence electron; NHC = N-heterocyclic carbene) is reported and compared to the chemistry of the corresponding nickel complex. Quantum chemical analyses reveal that differences in the reactivity of group 10 NHC complexes are caused by differences in the rigidity and thus activation strain associated with bending the corresponding d-[M(NHC)] fragments during reaction. These results should have implications for the understanding of the fundamental steps in catalytic cycles, in which such complex fragments are employed.
View Article and Find Full Text PDFSteric nature of the bite angle. A closer and a broader look.
Dalton Trans
March 2011
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Scheikundig Laboratorium der Vrije Universiteit, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
The bite angle (ligand-metal-ligand angle) is known to greatly influence the activity of catalytically active transition-metal complexes towards bond activation. Here, we have computationally explored how and why the bite angle has such effects in a wide range of prototypical C-X bonds and palladium complexes, using relativistic density functional theory at ZORA-BLYP/TZ2P. Our model reactions cover the substrates H(3)C-X (with X = H, CH(3), Cl) and, among others, the model catalysts, Pd[PH(2)(CH(2))(n)PH(2)] (with n = 2-6) and Pd[PR(2)(CH(2))(n)PR(2)] (n = 2-4 and R = Me, Ph, t-Bu, Cl), Pd(PH(3))X(-) (X = Cl, Br, I), as well as palladium complexes of chelating and non-chelating N-heterocyclic carbenes.
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