Titanium(IV) Chloride

Gundersen, Lise‐Lotte; Rise, Frode; Undheim, Kjell; Aguilar, Enrique; García‐García, Patricia

doi:10.1002/047084289x.rt119.pub2

Cited by 1 publication

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“…Thus, the organometallic chemistry of titanium complexes attracts considerable attention for their distinct performance in olefin polymerization, catalysis and various organic synthesis. [ 2 ] For example, high‐valent Ti IV ‐complexes usually act as competent Lewis acids owing to their electropositive and oxophilic nature, [ 3 ] while low‐valent species, especially for some Ti II ‐species are highly reducing and applied for redox transformations, such as Kulinkovich reaction and Pauson‐ Khand reaction. [ 4 ] However, mechanistic studies on elementary reactions to elaborate titanium reactivity with different oxidation states are far behind while essential, which may inspire the development of catalytic systems with reversible Ti II /Ti IV cycles.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Mechanistic Studies on Programmed C―O/C―H Activation with Valence‐Adjusted Ti‐Complexes

et al. 2023

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Comprehensive SummaryTwo‐electron reduction of [N2NBn]TiIVCl2 (3) gave a highly reactive [N2N]TiII species, which underwent C—O bond activation of THF (tetrahydrofuran) to generate [N2NBn]TiIV[O(CH2)4] (4) through oxidative addition. The resulted TiIV–Csp3 bond in oxametallacyclohexane was tantamount to the elaborately‐designed Ti‐alkyl complexes, competent to activate intramolecular Csp2–H bond, forming ortho‐cyclometalated complex [N2NCH2C6H4]TiIV(OnBu) (5). Key intermediates were isolated and fully characterized by X‐ray crystallography. Mechanistic studies revealed that the oxidative addition of C—O bond took place at TiII‐center via a radical intermediate, while a Csp2–H bond activation proceeded by σ‐bond metathesis with a kitelike four‐centered TiIV‐transition state.

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Section: Background and Originality Contentmentioning

confidence: 99%