title: Orbital-Overlap control in the solid-state reactivity of beta-azido-propiophenones: selective formation of cis-azo-dimers.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, USA.
authors.forename: Jagadis
authors.initials: J
authors.lastname: Sankaranarayanan
authors.forename: Lauren N
authors.initials: LN
authors.lastname: Bort
authors.forename: Sarah M
authors.initials: SM
authors.lastname: Mandel
authors.forename: Ping
authors.initials: P
authors.lastname: Chen
authors.forename: Jeanette A
authors.initials: JA
authors.lastname: Krause
authors.forename: Elwood E
authors.initials: EE
authors.lastname: Brooks
authors.forename: Pearl
authors.initials: P
authors.lastname: Tsang
authors.forename: Anna D
authors.initials: AD
authors.lastname: Gudmundsdottir