title: Intermolecular C-H bond activation promoted by a titanium alkylidyne.
abstract: The transient titanium alkylidyne complex (PNP)TiCtBu (PNP = N-[2-P(CHMe2)2-4-methylphenyl]2-), prepared from alpha-hydrogen abstraction of the corresponding alkylidene-alkyl species (PNP)Ti=CHtBu(CH2tBu), can readily undergo intermolecular 1,2-addition of C-H bonds of benzene and SiMe4. Synthesis and reactivity, isotopic labeling, kinetics, and theoretical studies strongly favor an alkylidyne pathway and the alpha-H abstraction step to be the rate-determining step.
authors.affiliation: Department of Chemistry, Molecular Structure Center and School of Informatics, Indiana University, Bloomington, Indiana 47405, USA.
authors.forename: Brad C
authors.initials: BC
authors.lastname: Bailey
authors.forename: Hongjun
authors.initials: H
authors.lastname: Fan
authors.forename: Erich W
authors.initials: EW
authors.lastname: Baum
authors.forename: John C
authors.initials: JC
authors.lastname: Huffman
authors.forename: Mu-Hyun
authors.initials: MH
authors.lastname: Baik
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Mindiola
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D001554:Benzene / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D014025:Titanium / Q000737:chemistry*
chemical_list: D000480:Alkynes; D002244:Carbon; D006859:Hydrogen; D014025:Titanium; D001554:Benzene