Room temperature ring-opening metathesis of pyridines by a transient Ti[triple bond]C linkage.
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.
Bailey
Brad C
BC
Department of Chemistry, Molecular Structure Center and School of Informatics, Indiana University, Bloomington, IN 47405, USA.
Fan
Hongjun
H
Huffman
John C
JC
Baik
Mu-Hyun
MH
Mindiola
Daniel J
DJ
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
D011725:Pyridines; D002244:Carbon; D014025:Titanium; D009584:Nitrogen