906357-55-9Relevant academic research and scientific papers
Oxidatively induced ??-hydrogen abstraction. A mild protocol to generate terminal titanium alkylidenes containing a β-hydrogen
Bailey, Brad C.,Basuli, Falguni,Huffman, John C.,Mindiola, Daniel J.
, p. 3963 - 3968 (2006)
One-electron oxidation of the Ti(III) bis-isobutyl complexes (nacnac)Ti(CH2iPr)2 (1) (nacnac- = [ArNC(tBu)]2CH, Ar = 2,6-iPr2C 6H3) and (PNP)Ti(CH2iPr)2 (4) (PNP- = N[2-P(CHMe2)2-4-methylphenyl] 2) with AgOTf promotes exclusive α-hydrogen abstraction to provide the first structurally characterized examples of terminal group 4 alkylidenes bearing a β-hydrogen, namely, (nacnac)Ti=CHiPr(OTf) (2) and (PNP)Ti=CHiPr(OTf) (5). These complexes have been prepared and characterized by means of multinuclear NMR spectroscopy as well as single-crystal X-ray diffraction analysis. In the case of the nacnac framework, the reactive Ti=CHiPr motif can readily engage in an intramolecular Wittig-like rearrangement. However, the isobutylidene motif can be stabilized when supported by a more robust ancillary ligand such as PNP, which is demonstrated by the thermal resistance of 5 and the preparation of a rare example of a stable alkylidene methyl complex (PNP)Ti=CHiPr(Me) (6).
