Issue 40, 2016

Metallo-Wittig chemistry of an alkylidene to form a terminal titanium oxo complex

Abstract

We report the synthesis and structure of a titanium(IV) benzophenone adduct bearing a terminal oxo ligand, (PNP)Ti = O(OTf)(OCPh2) (PNP = N[2-PiPr2-4-methylphenyl]2) (2). Complex 2 is readily synthesized in 71% yield from the previously reported titanium alkylidene (PNP)Ti[double bond, length as m-dash]CHtBu(OTf) (1) and two equivalents of benzophenone, by extruding the olefin Ph2C[double bond, length as m-dash]CHtBu. Treatment of benzophenone adduct 2 with a bulky aryloxide salt results in formation of (PNP)Ti[double bond, length as m-dash]O(OAr) (3) (OAr = 2,6-bis(diphenylmethyl)-4-tert-butylphenoxide), concurrent with salt elimination and displacement of the benzophenone. Complexes 2 and 3 were characterized by single-crystal X-ray diffraction and a variety of spectroscopic techniques, including NMR, UV-Vis-NIR spectroscopies, and TD-DFT calculations.

Graphical abstract: Metallo-Wittig chemistry of an alkylidene to form a terminal titanium oxo complex

Supplementary files

Article information

Article type
Paper
Submitted
21 Apr. 2016
Accepted
13 Jūn. 2016
First published
13 Jūn. 2016

Dalton Trans., 2016,45, 15894-15901

Metallo-Wittig chemistry of an alkylidene to form a terminal titanium oxo complex

D. P. Solowey, T. Kurogi, B. C. Manor, P. J. Carroll and D. J. Mindiola, Dalton Trans., 2016, 45, 15894 DOI: 10.1039/C6DT01534D

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