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Issue 21, 2013
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Supramolecular bulky phosphines comprising 1,3,5-triaza-7-phosphaadamantane and Zn(salphen)s: structural features and application in hydrosilylation catalysis

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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.

Graphical abstract: Supramolecular bulky phosphines comprising 1,3,5-triaza-7-phosphaadamantane and Zn(salphen)s: structural features and application in hydrosilylation catalysis

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Article information


Submitted
09 Jan 2013
Accepted
18 Feb 2013
First published
20 Feb 2013

Dalton Trans., 2013,42, 7595-7603
Article type
Paper

Supramolecular bulky phosphines comprising 1,3,5-triaza-7-phosphaadamantane and Zn(salphen)s: structural features and application in hydrosilylation catalysis

D. Anselmo, R. Gramage-Doria, T. Besset, M. V. Escárcega-Bobadilla, G. Salassa, E. C. Escudero-Adán, M. Martínez Belmonte, E. Martin, J. N. H. Reek and A. W. Kleij, Dalton Trans., 2013, 42, 7595
DOI: 10.1039/C3DT00078H

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