3992794

Unique synthesis and fluxional solution behavior of titanium(IV) trityl imidos supported by a bulky tris-pyrazolylborate ligand | Poster Board #940

Date
March 17, 2024
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In expanding the reactivity of our previously reported pseudo-tetrahedral TiII complex TptBu,MeTiCl (1) (TptBu,Me = hydridotris(3-tert-butyl-5-methylpyrazol-1-yl)borate), we explored its reactivity with bulky organic azides and lithium anilides. To that end, we report a bifurcated synthetic pathway to a terminal TiIV imido which, upon mild heating, undergoes a sigmatropic rearrangement via a 1,2-borotropic shift. Unique to this system, the kinetic product containing a C3 symmetric Tp ligand can be isolated and characterized prior to inducing the 1,2-borotropic shift by mild heating. The rearrangement mechanism is proposed by kinetic data obtained from variable temperature 1H NMR spectroscopy. Additionally, upon reaction of 1 with bulky lithium anilides, the formation of H2 is observed in a unique example of N-H bond activation to form a ligand cyclometallated TiIV terminal imido.

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Speaker

Speaker Image for Daniel Mindiola
University of Pennsylvania

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