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• W2318564382 startingPage "1039" @default.
• W2318564382 abstract "The six-coordinate molybdenum(IV) oxido isocyanide complex 1 [Δ,Λ-OC-6-2-3-[MoO(Np∩Ni)2(CNtBu)]; Np∩Ni = 4-tert-butylphenyl(pyrrolato-2-ylmethylene)amine] is obtained in diastereomerically pure form in the solid state, as revealed by single-crystal X-ray diffraction. In solution, this stereoisomer equilibrates with the Δ,Λ-OC-6-2-4 diastereomer 2 at ambient temperature. The stereochemistry of both isomers has been elucidated by NMR, IR, and UV/vis spectroscopy in combination with density functional theory (DFT)/polarizable continuum model and time-dependent DFT calculations. The isomerization 1 → 2 is suggested to proceed via a dissociative trigonal twist with dissociation of the imine nitrogen donor Ni of one chelate ligand (hemilabile ligand) rather than dissociation of the monodentate isocyanide ligand. The isomerization barrier has been experimentally determined as 91 and 95 kJ mol–1 in tetrahydrofuran and toluene, respectively." @default.
• W2318564382 created "2016-06-24" @default.
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• W2318564382 date "2014-01-06" @default.
• W2318564382 modified "2023-09-30" @default.
• W2318564382 title "Ligand Dynamics of <i>tert</i>-Butyl Isocyanide Oxido Complexes of Molybdenum(IV)" @default.
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• W2318564382 doi "https://doi.org/10.1021/ic4025102" @default.
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