(N, Se) and (Se, N, Se) Ligands Based on Carborane and Pyridine Fragments – Reactivity of 2, 6‐[(1′‐Me‐1′, 2′‐closo‐C2B10H10)SeCH2]2C5H3N towards Copper and Silver. Issue 20 (29th May 2017)

• Record Type: Journal Article
• Authors: Ilie, Adriana; Crespo, Olga; Gimeno, M. Concepción; Holthausen, Max C.; Laguna, Antonio; Diefenbach, Martin; Silvestru, Cristian
• Is Part Of: European journal of inorganic chemistry. Issue 20(2017)
• Page Start: 2643
• Page End: 2652
• Publication Date: 2017-05-29
• Subjects: Carboranes -- Copper -- Silver -- Hydrogen bonds -- Selenolates; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700075
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Two new closo ‐carborane selenolated ligands, 2‐[(1′‐Me‐1′, 2′‐ closo ‐C2 B10 H10 )SeCH2 ]C5 H4 N (L 1 ) and 2, 6‐[(1′‐Me‐1′, 2′‐ closo ‐C2 B10 H10 )SeCH2 ]2 C5 H3 N (L 2 ), were prepared by the C–H activation of 1‐Me‐1, 2‐C2 B10 H11 with n BuLi, followed by the insertion of elemental selenium into the C–Li bond and reaction with 2‐(BrCH2 )C5 H4 N or 2, 6‐(BrCH2 )2 C5 H3 N, respectively. The closo speciesL 1 andL 2 were deboronated with CsF to give the nido ‐carborane cesium salts Cs[2‐{(1′‐Me‐1′, 2′‐ nido ‐C2 B9 H9 )SeCH2 }C5 H4 N] (1 ) and Cs2 [2, 6‐{(1′‐Me‐1′, 2′‐ nido ‐C2 B9 H9 )SeCH2 }2 C5 H3 N] (2 ). The isolation of the complexes [Ag(OTf)(L 2 )] (3, OTf = triflate), [Ag(PPh3 )(L 2 )][OTf] (4 ), [Cu(L 2 )(MeCN)][PF6 ] (5 ), and [Cu(L 2 )2 ][PF6 ] (6 ) indicates the coordination ability ofL 2 towards these metals. The molecular structures ofL 1 andL 2 were established by single‐crystal X‐ray diffraction. Quantum‐chemical calculations confirmed the molecular geometries and also the presence of C–H··· Se intramolecular interactions as well as C–H··· H–B and B–H··· π intermolecular interactions. Abstract : New closo ‐carborane selenolated ligands, 2‐[(1′‐Me‐1′, 2′‐ closo ‐C2 B10 H10 )SeCH2 ]C5 H4 N (L 1 ) and 2, 6‐[(1′‐Me‐1′, 2′‐ closo ‐C2 B10 H10 )SeCH2 ]2 C5 H3 N (L 2 ), are prepared, and their molecular structures are established by single‐crystal X‐ray diffraction. The reactivity of the versatile, potential polydentate ligandL 2 is investigated towards silver(I) and copper(I) cations.