title: Copper(I)-induced amplification of a [2]catenane in a virtual dynamic library of macrocyclic alkenes.
abstract: Olefin cross-metathesis of diluted dichloromethane solutions (≤0.15 M) of the 28-membered macrocyclic alkene C1, featuring a 1,10-phenanthroline moiety in the backbone, as well as of catenand 1, composed of two identical interlocked C1 units, generates families of noninterlocked oligomers Ci. The composition of the libraries is strongly dependent on the monomer concentration, but independent of whether C1 or 1 is used as feedstock, as expected for truly equilibrated systems. Accordingly, the limiting value 0.022 M approached by the equilibrium concentration of C1 when the total monomer concentration approaches the critical value, as predicted by the Jacobson-Stockmayer theory, provides a reliable estimate of the thermodynamically effective molarity. Catenand 1 behaves as a virtual component of the dynamic libraries, in that there is no detectable trace of its presence in the equilibrated mixtures, but becomes the major component - in the form of its copper(I) complex - when olefin cross-metathesis is carried out in the presence of a copper(I) salt.
authors.affiliation: Dipartimento di Chimica, Sapienza Università di Roma and Istituto CNR di Metodologie Chimiche (IMC-CNR), Sezione Meccanismi di Reazione, c/o Dipartimento di Chimica, Sapienza Università di Roma, P.le A. Moro 5, I-00185 Rome, Italy. stefano.distefano@uniroma1.it.
authors.forename: José Augusto
authors.initials: JA
authors.lastname: Berrocal
authors.forename: Marko M L
authors.initials: MM
authors.lastname: Nieuwenhuizen
authors.forename: Luigi
authors.initials: L
authors.lastname: Mandolini
authors.forename: E W
authors.initials: EW
authors.lastname: Meijer
authors.forename: Stefano
authors.initials: S
authors.lastname: Di Stefano