Orbital-Overlap control in the solid-state reactivity of beta-azido-propiophenones: selective formation of cis-azo-dimers.
Solid-state photolysis of 1a,b yields selectively cis-3a,b. X-ray analysis of 1a,b reveals the molecules adopt an extended structure and as such the crystal packing arrangement consists of planar, pi-stacked molecules. The shortest intermolecular distance between adjacent N-atoms is approximately 3.76 A and would lead to formation of trans-3a,b, whereas cis-3a,b is formed by dimerization between N-atoms that are approximately 3.9 A apart. We propose that the molecular orbital alignment of the adjacent nitrenes controls the solid-state reactivity.
Sankaranarayanan
Jagadis
J
Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, USA.
Bort
Lauren N
LN
Mandel
Sarah M
SM
Chen
Ping
P
Krause
Jeanette A
JA
Brooks
Elwood E
EE
Tsang
Pearl
P
Gudmundsdottir
Anna D
AD