Improved syntheses, and structural and electronic characterization of carboxamide-substituted TpCONHPh,Me and TpCONHt-Bu,Me ligands

• Published in: Acta crystallographica. Section C, Crystal structure communications Crystal structure communications, 2013-09, Vol.69 (9), p.947-953
• Main Authors: Sirianni, Eric R., Yap, Glenn P. A., Akturk, Eser S., Theopold, Klaus H.
• Format: Article
• Language: English
• Subjects: Carbonyls; Chemical bonds; Chemical compounds; Chemical synthesis; Crystal structure; Crystallography; crystals structure; Displays; Electronics; Hydrogen bonding; Ligands; scorpionates; Solvents; Tetrahydrofuran
• ISSN: 0108-2701; 1600-5759
• DOI: 10.1107/S0108270113015898

Improvements in the syntheses of the carboxamide‐substituted tris(pyrazolyl)borate ligands TpCONHPh,Me [tris(3‐anilinocarbonyl‐5‐methylpyrazol‐1‐yl)borate] and TpCONHt‐Bu,Me [tris(3‐tert‐butylaminocarbonyl‐5‐methylpyrazol‐1‐yl)borate] are reported. Their TlI salts, namely [tris(3‐anilinocarbonyl‐5‐methylpyrazol‐1‐yl‐κN2)borato]thallium(I), [Tl(C33H31BN9O3)], (II), and [tris(3‐tert‐butylaminocarbonyl‐5‐methylpyrazol‐1‐yl‐κN2)borato]thallium(I), [Tl(C27H43BN9O3)], (III), as well as the CuI carbonyl complexes (TpCONHPh,Me)Cu(CO), namely carbonyl[tris(3‐anilinocarbonyl‐5‐methylpyrazol‐1‐yl‐κN2)borato]copper(I) tetrahydrofuran trisolvate, [Cu(C33H31BN9O3)(CO)]·3C4H8O, (IV), and (TpCONHt‐Bu,Me)Cu(CO), namely carbonyl[tris(3‐tert‐butylaminocarbonyl‐5‐methylpyrazol‐1‐yl‐κN2)borato]copper(I) tetrahydrofuran hemisolvate, [Cu(C27H43BN9O3)(CO)]·0.5C4H8O, (V), have been prepared. Their spectroscopic properties and structures are compared with those of related compounds. The molecules of (II)–(V) show hydrogen bonding to either solvent molecules or neighboring complex molecules via amide groups. The title compounds feature the ability to engage other ligands in hydrogen bonding and they show strong electron‐withdrawing character. Compound (V) displays voids of ca 800 Å3 in the crystal structure.