Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons

Grasruck A, Parla G, Heinemann FW, Langer J, Herrera AC, Friess S, Schmid G, Dorta R (2022)

Publication Type: Journal article

Publication year: 2022

Journal

DOI: 10.1039/d2nj05222a

Abstract

The new mono dibenzo[b,f]-azepinyl substituted P-alkene ligands 7-9, 20, and 21 were used to synthesize monomeric and dimeric Cu(i) complexes by using metal to ligand ratios of 2 : 1 and 1 : 1, respectively. With the super-bulky tris dibenzo[b,f]-azepinyl substituted P-alkenes 21, only monomers form with a 1 : 1 stoichiometry. Cationic complexes were obtained either by employing [Cu(OTf)](2)& BULL;C6H6 as the starting material, or by chloride abstractions from the monomeric chlorido complexes with NaB(Ar-F)(4) or TlBF4, whereas with silver salts only Ag(i)-P-alkene complexes were isolated by transmetallation. Chloride abstraction with NaB(Ar-F)(4) gave the 14 ve cationic complex 18, which shows no alkene coordination and a bent coordination geometry due to the steric pressure exerted by the ligand. The buried volumes of the ligands (calculated from X-ray diffraction data) increase in the order 8 < 7 < 9 < 20 < 21 with the last displaying a staggering V-bur of 60.6% (the crystallographic Tolman angle in copper complex 23 amounts to 229 & DEG;). The bulkiest ligand (21) allowed us to isolate and structurally characterize rare examples of 14 ve Cu(i) complexes, namely the neutral chloride 23 and, after salt metathesis with NaB(Ar-F)(4), the chlorido bridged dinuclear cation 26 exhibiting short Cu-Cl bonds.

Authors with CRIS profile

Involved external institutions

Siemens Energy Global GmbH & Co. KG Germany (DE)

How to cite

APA:

Grasruck, A., Parla, G., Heinemann, F.W., Langer, J., Herrera, A.C., Friess, S.,... Dorta, R. (2022). Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons. New Journal of Chemistry. https://doi.org/10.1039/d2nj05222a

MLA:

Grasruck, Alexander, et al. "Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons." New Journal of Chemistry (2022).

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