Copper(I) Complexes of Naphthyl‐Substituted Fluorinated Trispyrazolylborate Ligands with Ethene and Carbon Monoxide. Issue 15 (9th March 2016)

• Record Type: Journal Article
• Authors: van Dijkman, Thomas F.; Siegler, Maxime A.; Bouwman, Elisabeth
• Other Names: Pettinari C. guestEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 15/16(2016)
• Page Start: 2586
• Page End: 2594
• Publication Date: 2016-03-09
• Subjects: Copper -- Carbon monoxide -- Ethene -- Scorpionate ligands; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201600015
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Four Cu I complexes of the two new hydridotrispyrazolylborate ligands hydridotris[3‐trifluoromethyl‐5‐(1‐naphthyl)pyrazol‐1‐yl]borate (= [Tp CF3, 1Nt ] – ) and hydridotris[3‐trifluoromethyl‐5‐(2‐naphthyl)pyrazol‐1‐yl]borate (= [Tp CF3, 2Nt ] – ) have been synthesized by reaction of the sodium salts of the ligands with CuI under either ethene or carbon monoxide atmosphere. Single crystal X‐ray diffraction analyses yielded the molecular structures of the three compounds [Na2 (Tp CF3, 1Nt )2 (µ‐acetone)2 ], [Cu(Tp CF3, 1Nt )(C2 H4 )] and [Cu(Tp CF3, 2Nt )(C2 H4 )]. The Cu I ions are in approximate tetrahedral geometries comprising the three nitrogen donors of the tridentate ligand and the η 2 ‐coordinated ethene ligands. The sodium ion in [Na2 (Tp CF3, 1Nt )2 (µ‐acetone)2 ] is found in a distorted octahedral coordination geometry formed by three N‐donors of the facially coordinating tridentate ligand, two O‐donors of bridging acetone ligands and a fluoride of a bridging –CF3 group with a particularly short Na··· F distance. The chemical shifts of the ethene ligands in [Cu(Tp CF3, 1Nt )(C2 H4 )] and [Cu(Tp CF3, 2Nt )(C2 H4 )] are 5.00 ppm and 4.96 ppm respectively on 1 H‐NMR and 85.9 ppm and 85.8 ppm on 13 C‐NMR spectroscopy. The CO stretching frequencies in the IR spectra of [Cu(Tp CF3, 1Nt )(CO)] and [Cu(Tp CF3, 2Nt )(CO)] are found at 2103 and 2109 cm –1, respectively. Abstract : The structures of the Cu I complexes of the two new ligands hydridotris[3‐trifluoromethyl‐5‐( n ‐naphthyl)pyrazol‐1‐yl]borate ( n = 1, [Tp CF3, 1Nt ] – ; n = 2, [Tp CF3, 2Nt ] – ) show essentially equal binding pockets. The surprising differences in the electron density on the Cu I ions must therefore be the result of different conformations of the 1‐ and 2‐naphthyl groups.