Ruthenium(II)-Mediated Carbon−Carbon Bond
Formation between Acetonitrile and Pyrrole: Combined
Experimental and Computational Study
Karl A. Pittard
Thomas R. Cundari
T. Brent Gunnoe
Cynthia S. Day
Jeffrey L. Petersen
10.1021/om0506668.s005
https://acs.figshare.com/articles/journal_contribution/Ruthenium_II_Mediated_Carbon_Carbon_Bond_Formation_between_Acetonitrile_and_Pyrrole_Combined_Experimental_and_Computational_Study/3264118
The reaction of TpRu(CO)(NCMe)(Me) (<b>1</b>) and pyrrole forms TpRu(CO){κ<sup>2</sup>-<i>N,N</i>-(H)NC(Me)(NC<sub>4</sub>H<sub>3</sub>)} (<b>2</b>). The formation of complex <b>2</b> involves the cleavage of the N−H bond and
2-position C−H bonds of pyrrole as well as a C−C bond forming step between pyrrole and
the acetonitrile ligand of <b>1</b>. Mechanistic studies indicate that the most likely reaction pathway
involves initial metal-mediated N−H activation of pyrrole to produce TpRu(CO)(<i>N</i>-pyrrolyl)(NCMe) (<b>3</b>) followed by C−C bond formation and proton transfer. Complex <b>3</b> has been
independently prepared and demonstrated to convert to <b>2</b>. Computational studies support
the suggested selectivity for initial N−H bond cleavage in preference to C−H bond activation.
2005-10-10 00:00:00
Computational studies support
Computational Study
pyrrole
TpRu
proton transfer
Mechanistic studies
acetonitrile ligand
Complex 3
reaction pathway
bond