title: Supramolecular bulky phosphines comprising 1,3,5-triaza-7-phosphaadamantane and Zn(salphen)s: structural features and application in hydrosilylation catalysis.
abstract: The use of the commercially available, bifunctional phosphine 1,3,5-triaza-7-phosphaadamantane (abbreviated as PN3) in conjunction with a series of Zn(salphen) complexes leads to sterically encumbered phosphine ligands as a result of (reversible) coordinative Zn-N interactions. The solid state and solution phase behaviour of these supramolecular ligand systems have been investigated in detail and revealed their stoichiometries in the solid state observed by X-ray crystallography, and those determined in solution by NMR and UV-Vis spectroscopy. Also, upon application of these supramolecular bulky phosphines in hydrosilylation catalysis employing 1-hexene as a substrate, the catalysis data infer the presence of an active Rh species with two coordinated, bulky PN3/Zn(salphen) assembly units having a maximum of three Zn(salphen)s associated per PN3 scaffold, with an excess of bulky phosphines hardly affecting the overall activity.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 - Tarragona, Spain.
authors.forename: Daniele
authors.initials: D
authors.lastname: Anselmo
authors.forename: Rafael
authors.initials: R
authors.lastname: Gramage-Doria
authors.forename: Tatiana
authors.initials: T
authors.lastname: Besset
authors.forename: Martha V
authors.initials: MV
authors.lastname: Escárcega-Bobadilla
authors.forename: Giovanni
authors.initials: G
authors.lastname: Salassa
authors.forename: Eduardo C
authors.initials: EC
authors.lastname: Escudero-Adán
authors.forename: Marta
authors.initials: M
authors.lastname: Martínez Belmonte
authors.forename: Eddy
authors.initials: E
authors.lastname: Martin
authors.forename: Joost N H
authors.initials: JN
authors.lastname: Reek
authors.forename: Arjan W
authors.initials: AW
authors.lastname: Kleij