Substituent effects in pyridyl-functionalized pyrylium salts, pyridines and λ<sup>3</sup>,σ<sup>2</sup>-phosphinines

a fundamental and systematic study

Journal article (2018)

Authors

Antonia Loibl Freie Universität Berlin
Wiebke Oschmann Freie Universität Berlin
Maria Vogler Freie Universität Berlin
E.A. Pidko ITMO University
Manuela Weber Freie Universität Berlin
Jelena Wiecko Freie Universität Berlin
Christian Müller Freie Universität Berlin
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Published Date

2018

Language

English

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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 and 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-phosphinine- and the bipyridine-based compounds. Their characterization by means of IR-spectroscopy gave experimental insight into the electronic properties of the respective ligands.