Journalartikel

σ‐ or π‐Coordination? Complexes of Univalent Gallium Salts with Aromatic Nitrogen Bases


AutorenlisteLichtenthaler, MR; Stahl, F; Kratzert, D; Benkmil, B; Wegner, HA; Krossing, I

Jahr der Veröffentlichung2014

Seiten4335-4341

ZeitschriftEuropean Journal of Inorganic Chemistry

Bandnummer2014

Heftnummer26

ISSN1434-1948

DOI Linkhttps://doi.org/10.1002/ejic.201402360

VerlagWiley-VCH Verlag


Abstract
To answer the question as to whether gallium in its oxidation state +1 favors a sigma- or a pi-coordination of aromatic nitrogen bases, we reacted [Ga(C6H5F)(2)](+)[Al(ORF)(4)](-) {R-F = C(CF3)} with pyrazine and 2,6-di-tert-butyl-4-methylpyridine (DTBMP). In doing so, we obtained the first tricoordinate, nonchelated, homoleptic N-donor complex of gallium(I): [Ga-(pyrazine)(3)](+)[Al(ORF)(4)](-), in which each gallium(I) cation is coordinated in a trigonal-pyramidal fashion by three eta(1)-donating pyrazine ligands. Hence, the gallium(I) cations favor sigma- over pi-coordination. Depending on the reaction conditions, and due to the bifunctionality of pyrazine, 1D coordination polymers of {[Ga(mu-pyrazine)(2)(eta(1)-pyrazine)](+)[Al(ORF)(4)](-)}(infinity) were also obtained. With the sterically demanding DTBMP, which is conventionally used as a proton scavenger, the mixed complex [Ga(C6H5F)(2)(DTBMP)](+)[Al(ORF)(4)](-) was isolated, thus proving incorrect the perception of DTBMP being "non-nucleophilic". The structural findings were confirmed by multinuclear NMR investigations and density functional performed at the RI-BP86/SV(P) level.



Zitierstile

Harvard-ZitierstilLichtenthaler, M., Stahl, F., Kratzert, D., Benkmil, B., Wegner, H. and Krossing, I. (2014) σ‐ or π‐Coordination? Complexes of Univalent Gallium Salts with Aromatic Nitrogen Bases, European Journal of Inorganic Chemistry, 2014(26), pp. 4335-4341. https://doi.org/10.1002/ejic.201402360

APA-ZitierstilLichtenthaler, M., Stahl, F., Kratzert, D., Benkmil, B., Wegner, H., & Krossing, I. (2014). σ‐ or π‐Coordination? Complexes of Univalent Gallium Salts with Aromatic Nitrogen Bases. European Journal of Inorganic Chemistry. 2014(26), 4335-4341. https://doi.org/10.1002/ejic.201402360


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