Intermolecular C-H bond activation promoted by a titanium alkylidyne.
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.
Bailey
Brad C
BC
Department of Chemistry, Molecular Structure Center and School of Informatics, Indiana University, Bloomington, Indiana 47405, USA.
Fan
Hongjun
H
Baum
Erich W
EW
Huffman
John C
JC
Baik
Mu-Hyun
MH
Mindiola
Daniel J
DJ
D000480:Alkynes / Q000737:chemistry*; D001554:Benzene / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D014025:Titanium / Q000737:chemistry*
D000480:Alkynes; D002244:Carbon; D006859:Hydrogen; D014025:Titanium; D001554:Benzene