Monomeric, Divalent Vanadium Bis(arylamido) Complexes: Linkage Isomerism and Reactivity
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https://figshare.com/articles/dataset/Monomeric_Divalent_Vanadium_Bis_arylamido_Complexes_Linkage_Isomerism_and_Reactivity/7848275
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资源简介：
Divalent complexes
of vanadium were synthesized employing bulky
silyl(aryl)amido ligands −N(SiiPr3)DIPP and −N(SitBu2Me)DIPP (DIPP = 2,6-iPr2C6H3). Solid-state structural characterization
revealed that although the ligand −N(SiiPr3)DIPP supports a monomeric, bis(amido) complex
of vanadium, its constitutional isomer −N(SitBu2Me)DIPP affords a homoleptic complex in which
the vanadium center is sandwiched between the arene rings, an unusual
binding mode for arylamido ligands. Magnetometry studies indicate
that V[N(SiiPr3)DIPP]2 and V[(η5-DIPP)N(SitBu2Me)]2 have similar high-spin d3 electron configurations. However, spectroscopic methods, including
electron paramagnetic resonance, nuclear magnetic resonance, infrared,
and UV–visible spectroscopies, in addition to cyclic voltammetry
and reactivity studies, suggest that V[N(SiiPr3)DIPP]2 is stereochemically nonrigid
in solution, while V[(η5-DIPP)N(SitBu2Me)]2 is not. This nonrigidity explicitly
impacts the reactivity of V[N(SiiPr3)DIPP]2, which can be used to access both amido-bound
and arene-bound complexes. Moreover, treatment of V[N(SiiPr3)DIPP]2 with single and
multielectron oxidants reveals a range of transformations including
an intramolecular sp3 C–H bond activation.
创建时间：
2019-03-14
