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Substituent Effects in Pyridyl-Functionalized Pyrylium Salts, Pyridines and λ3,σ2-Phosphinines: A Fundamental and Systematic Study

Abstract

A series of substituted, pyridyl-functionalized 2,4,6-triarylpyrylium salts were prepared and investigated for their light absorption and emission properties. After reaction with P(SiMe3)3 the corresponding λ3-phosphinines were obtained, which carry on the 4- or 6-aryl ring +/-I and +/- M substituents. Supported by DFT calculations a systematic evaluation of the σ-donor, π-donor as well as π-acceptor properties of these low-coordinate P,N-hybrid ligands was performed. The modular synthetic approach allowed us at the same time to synthesize the structurally related bipyridine-derivatives for comparison reasons. Reaction of the chelating ligands with [W(CO)6] in THF afforded the corresponding [(P^N)W(CO)4] and [(N^N)W(CO)4] complexes. A crystallographic characterization of selected coordination compounds revealed significant structural differences between the pyridyl-phosphinines- and the bipyridine-based compounds. Their characterization by means of IR-spectroscopy gave experimental insight into the electronic properties of the respective ligands.

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Publication details

The article was received on 12 Apr 2018, accepted on 07 Jun 2018 and first published on 13 Jun 2018


Article type: Paper
DOI: 10.1039/C8DT01441H
Citation: Dalton Trans., 2018, Accepted Manuscript
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    Substituent Effects in Pyridyl-Functionalized Pyrylium Salts, Pyridines and λ3,σ2-Phosphinines: A Fundamental and Systematic Study

    A. Loibl, W. Oschmann, M. Vogler, E. A. Pidko, M. Weber, J. Wiecko and C. Muller, Dalton Trans., 2018, Accepted Manuscript , DOI: 10.1039/C8DT01441H

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