C(sp3)−H Oxidative Addition and Transfer Hydrogenation Chemistry of a Titanium(II) Synthon: Mimicry of Late‐Metal Type Reactivity |
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| Authors: | J Rolando Aguilar‐Calderón Dr Alejandro J Metta‐Magaña Dr Bruce Noll Prof?Dr Skye Fortier |
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| Institution: | 1. http://utminers.utep.edu/asfortier/;2. Department of Chemistry, University of Texas at El Paso, El Paso, TX, USA;3. Bruker AXS Inc., Madison, WI, USA |
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| Abstract: | Two‐electron reduction of the TiIV compound (ketguan)(ImDippN)Ti(OTf)2 ( 3 ) gives the arene‐masked complex (ketguan)(η6‐ImDippN)Ti ( 1 ) in excellent yield. Upon standing in solution, 1 converts to a TiIV metallacycle ( 4 ) through dehydrogenation of a pendant isopropyl group. Spectroscopic evidence shows this transformation initially proceeds via the oxidative addition of a C(sp3)?H bond and can be reversed upon exposure of 4 to H2. Interestingly, treatment of 1 with cyclohexene gives cyclohexane and 4 via a titanium‐mediated transfer hydrogenation reaction, a process that can be extended to catalytically hydrogenate other unsaturated hydrocarbons under mild conditions. These results, rare for the early‐metals, suggest 1 possesses chemical characteristics reminiscent of noble, late‐metals. |
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| Keywords: | C− H activation N ligands reduction titanium transfer hydrogenation |
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