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Issue 40, 2016
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Metallo-Wittig chemistry of an alkylidene to form a terminal titanium oxo complex

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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

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Publication details

The article was received on 21 Apr 2016, accepted on 13 Jun 2016 and first published on 13 Jun 2016


Article type: Paper
DOI: 10.1039/C6DT01534D
Citation: Dalton Trans., 2016,45, 15894-15901
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    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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