title: Room temperature ring-opening metathesis of pyridines by a transient Ti[triple bond]C linkage.
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 cleave the C-N bond of N-heterocycles such as pyridine and 4-picoline at room temperature to afford azametallabicyclic systems. Experimental and theoretical studies strongly favor a ring-opening metathesis pathway where [2 + 2] cycloaddition of pyridine across the TiC linkage ultimately leads to C-N bond rupture.
authors.affiliation: Department of Chemistry, Molecular Structure Center and School of Informatics, Indiana University, Bloomington, IN 47405, USA.
authors.forename: Brad C
authors.initials: BC
authors.lastname: Bailey
authors.forename: Hongjun
authors.initials: H
authors.lastname: Fan
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: D002244:Carbon / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods*; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry*; D013696:Temperature; D014025:Titanium / Q000737:chemistry
chemical_list: D011725:Pyridines; D002244:Carbon; D014025:Titanium; D009584:Nitrogen