Selective strong bond cleavage with a weak bond remaining intact is one of the most challenging subjects because it is generally quite difficult. The use of a transition metal complex is one of the most promising approaches to achieve selective strong bond cleavage.  This presentation shows several examples we have recently discovered where silyl migration in a coordination sphere serves as a trigger of strong bond cleavage.    Iron and molybdenum complexes can cleave C-CN bonds[1] in organonitriles (RCN), N-CN bonds[2] in cyanamides (R2NCN), and O-CN bond[2b,3] in cyanates (ROCN), even though these C-CN, N-CN, and O-CN bonds are strong and hence difficult to cleave. In these cases, the key step to achieve E-CN bond cleavage (E = C, N, O) is migration of a silyl group from a metal center to the nitrile nitrogen atom coordination to a transition metal in a hapto-2 bond fashion. The detail reaction mechanism will be discussed. References [1]  (a) Nakazawa, H.; Kawasaki, T.; Miyoshi, K.; Suresh, C. H.;  Koga, N. Organometallics 2004 , 23, 117. (b) Nakazawa, H.; Kamata, K.; Itazaki, M. Chem. Commun. 2005 , 4004. (c) Nakazawa, H.; Itazaki, M.; Kamata, K.; Ueda, K. Chem. Asian. J. 2007 , 2, 882.[2]   (a) Fukumoto, K.; Oya, T.; Itazaki, M.; Nakazawa, H. J. Am. Chem. Soc. 2009 , 131, 38. (b) Dahy, A. A.; Koga, N.; Nakazawa, H. Organometallics 2012 , 31, 3995. (c) Dahy, A. A.; Koga, N.; Nakazawa, H. Organometallics 2013 , 32, 2725.[3]   Fukumoto, K.; Dahy, A. A.; Oha, T.; Hayasaka, K.; Itazaki, M.; Koge, N.; Nakazawa, H. Organometallics, 2012 , 31, 787.

Selective bond cleavage catalyzed by a silyl complex of a transition metal

247th National Meeting (2014)

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