Structural trends in a series of bulky dialkylbiarylphosphane complexes of Cu^I

Abstract

CuI complexes containing the bulky dialkylbiarylphosphane 2-(di-tert-butylphosphanyl)-2′,4′,6′-triisopropylbiphenyl ( t BuXPhos, L) and an ancillary ligand (Cl−, Br−, I−, MeCN, ClO4 − or SCN−) have been structurally characterized, namely, chlorido[2-(di-tert-butylphosphanyl)-2′,4′,6′-triisopropylbiphenyl-κP]copper(I), [CuCl(C29H45P)], 1, bromido[2-(di-tert-butylphosphanyl)-2′,4′,6′-triisopropylbiphenyl-κP]copper(I), [CuBr(C29H45P)], 2, [2-(di-tert-butylphosphanyl)-2′,4′,6′-triisopropylbiphenyl-κP]iodidocopper(I), [CuI(C29H45P)], 3, (acetonitrile-κN)[2-(di-tert-butylphosphanyl)-2′,4′,6′-triisopropylbiphenyl-κP]copper(I) hexafluoridophosphate, [Cu(CH3CN)(C29H45P)]PF6, 4, [2-(di-tert-butylphosphanyl)-2′,4′,6′-triisopropylbiphenyl-κP](perchlorato-κO)copper(I), [Cu(ClO4)(C29H45P)], 5, and di-μ-thiocyanato-κ2 S:N;κ2 N:S-bis{[2-(di-tert-butylphosphanyl)-2′,4′,6′-triisopropylbiphenyl-κP]copper(I)}, [Cu2(NCS)2(C29H45P)2], 6. Iodide complex 3 shows significant CuI–arene interactions, in contrast to its chloride 1 and bromide 2 counterparts, which is attributed to the weaker interaction between the iodide ion and the CuI centre. When replacing iodide with an acetonitrile (in 4) or perchlorate (in 5) ligand, the reduced interaction between the CuI atom and the ancillary ligand results in stronger CuI–arene interactions. No CuI–arene interactions are observed in dimer 6, due to the tricoordinated CuI centre having sufficient electron density from the coordinated ligands.

Metallocyclic CuII–LnIII Single-Molecule Magnets from the Self-Assembly of 1,4-Diformylnaphthalene-2,3-diol

“…A combination of three transition metals and one lanthanide ion have, in the past, been used to template the macrocyclization of 2,3-dihydroxybenzene-1,4-dicarbaldehyde with various diamine linkers. − The Plieger group have previous experience in preparing multinuclear metal complexes with potentially interesting magnetic properties, − and the Ishida group have expertise in the magnetic characterization of 3d–4f complexes, particularly those involving copper­(II). − Inspired by the Zn 3 La system first reported by Nabeshima et al and later extended to other metal combinations by Brooker et al, ,,− we investigated the self-assembly and successful crystallization of L 3 Cu 3 Ln complexes using the acyclic ligand system 1,4-diformylnaphthalene-2,3-diol (H 2 L ). While there are numerous examples of magnetically coupled Cu–Ln systems, , throughout the literature, there are very few Cu 3 Ln complexes featuring four in-plane metal ions; − and a CCDC search indicated that, outside of the previously mentioned complexes of Nabeshima and Brooker, there are no other structurally characterized examples which exclusively contain Cu–O–Ln bridges.…”