title: Cluster-bound nitriles do not click with organic azides: unexpected formation of imino complexes of the [Re(6)(mu(3)-Se)(8)](2+) core-containing clusters.
abstract: The reactions of C(6)H(5)CH(CH(3))N(3) with nitrile solvates of the [Re(6)(mu(3)-Se)(8)](2+) core-containing cluster, [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(MeCN)](2+)(1) and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(MeCN)(2)](2+) (2), afforded the corresponding cationic imino complexes [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(PhN horizontal lineCHCH(3))](2+) (3) and cis-[Re(6)(mu(3)-Se)(8)(PEt(3))(4)(PhN horizontal lineCHCH(3))(2)](2+) (4), respectively. Both compounds were spectroscopically and crystallographically characterized. A mechanism involving a 1,2-shift of one of the groups on the azido alpha-C atom of the cluster-azide intermediate concerted with the photoexpulsion of dinitrogen of the azido ligand is invoked to rationalize the formation of the imino complexes. Density functional theory calculations showed that a cluster-to-ligand transition was responsible for the absorption that promotes the photodecomposition of the cluster-azide complex.
authors.affiliation: Department of Chemistry, University of Arizona, Tucson, Arizona 85721, USA.
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Tu
authors.forename: Ethan
authors.initials: E
authors.lastname: Boroson
authors.forename: Huong
authors.initials: H
authors.lastname: Truong
authors.forename: Alvaro
authors.initials: A
authors.lastname: Muñoz-Castro
authors.forename: Ramiro
authors.initials: R
authors.lastname: Arratia-Pérez
authors.forename: Gary S
authors.initials: GS
authors.lastname: Nichol
authors.forename: Zhiping
authors.initials: Z
authors.lastname: Zheng