title: C(sp3)-H Oxidative Addition and Transfer Hydrogenation Chemistry of a Titanium(II) Synthon: Mimicry of Late-Metal Type Reactivity.
abstract: Two-electron reduction of the TiIVcompound (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 TiIVmetallacycle (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.
authors.affiliation: Department of Chemistry, University of Texas at El Paso, El Paso, TX, 79968, USA.
authors.forename: J Rolando
authors.initials: JR
authors.lastname: Aguilar-Calderón
authors.affiliation: Department of Chemistry, University of Texas at El Paso, El Paso, TX, 79968, USA.
authors.forename: Alejandro J
authors.initials: AJ
authors.lastname: Metta-Magaña
authors.affiliation: Bruker AXS Inc., 5465 East Cheryl Parkway, Madison, WI, 53711, USA.
authors.forename: Bruce
authors.initials: B
authors.lastname: Noll
authors.affiliation: Department of Chemistry, University of Texas at El Paso, El Paso, TX, 79968, USA. asfortier@utep.edu.
authors.forename: Skye
authors.identifier: 0000-0002-0502-5229
authors.initials: S
authors.lastname: Fortier
keywords: C−H activation; N ligands; reduction; titanium; transfer hydrogenation