School of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North, New Zealand.
Acta Crystallogr C Struct Chem. 2021 Sep 1;77(Pt 9):513-521. doi: 10.1107/S2053229621008159. Epub 2021 Aug 16.
Cu complexes containing the bulky dialkylbiarylphosphane 2-(di-tert-butylphosphanyl)-2',4',6'-triisopropylbiphenyl (BuXPhos, L) and an ancillary ligand (Cl, Br, I, MeCN, ClO or SCN) have been structurally characterized, namely, chlorido[2-(di-tert-butylphosphanyl)-2',4',6'-triisopropylbiphenyl-κP]copper(I), [CuCl(CHP)], 1, bromido[2-(di-tert-butylphosphanyl)-2',4',6'-triisopropylbiphenyl-κP]copper(I), [CuBr(CHP)], 2, [2-(di-tert-butylphosphanyl)-2',4',6'-triisopropylbiphenyl-κP]iodidocopper(I), [CuI(CHP)], 3, (acetonitrile-κN)[2-(di-tert-butylphosphanyl)-2',4',6'-triisopropylbiphenyl-κP]copper(I) hexafluoridophosphate, [Cu(CHCN)(CHP)]PF, 4, 2-(di-tert-butylphosphanyl)-2',4',6'-triisopropylbiphenyl-κPcopper(I), [Cu(ClO)(CHP)], 5, and di-μ-thiocyanato-κS:N;κN:S-bis{[2-(di-tert-butylphosphanyl)-2',4',6'-triisopropylbiphenyl-κP]copper(I)}, [Cu(NCS)(CHP)], 6. Iodide complex 3 shows significant Cu-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 Cu centre. When replacing iodide with an acetonitrile (in 4) or perchlorate (in 5) ligand, the reduced interaction between the Cu atom and the ancillary ligand results in stronger Cu-arene interactions. No Cu-arene interactions are observed in dimer 6, due to the tricoordinated Cu centre having sufficient electron density from the coordinated ligands.
含有大位阻二烷基联苯膦 2-(二-叔丁基膦基)-2',4',6'-三异丙基联苯 (BuXPhos, L) 和辅助配体 (Cl、Br、I、MeCN、ClO 或 SCN) 的 Cu 配合物已被结构表征，即氯代[2-(二-叔丁基膦基)-2',4',6'-三异丙基联苯-κP] 一价铜 (I)，[CuCl(CHP)]，1，溴代[2-(二-叔丁基膦基)-2',4',6'-三异丙基联苯-κP] 一价铜 (I)，[CuBr(CHP)]，2，[2-(二-叔丁基膦基)-2',4',6'-三异丙基联苯-κP] 碘化铜 (I)，[CuI(CHP)]，3，(乙腈-κN)[2-(二-叔丁基膦基)-2',4',6'-三异丙基联苯-κP] 一价铜 (I) 六氟磷酸盐，[Cu(CHCN)(CHP)]PF，4，2-(二-叔丁基膦基)-2',4',6'-三异丙基联苯-κP 一价铜 (I)，[Cu(ClO)(CHP)]，5，和二-μ-硫氰酸根-κS:N；κN:S-双{[2-(二-叔丁基膦基)-2',4',6'-三异丙基联苯-κP] 一价铜 (I)}，[Cu(NCS)(CHP)]，6。与氯代物 1 和溴代物 2 相比，碘代物 3 显示出明显的 Cu-芳环相互作用，这归因于碘离子与 Cu 中心之间较弱的相互作用。当用乙腈 (在 4 中) 或高氯酸根 (在 5 中) 配体取代碘化物时，Cu 原子与辅助配体之间的相互作用减弱，导致更强的 Cu-芳环相互作用。在二聚体 6 中观察不到 Cu-芳环相互作用，因为配位的配体从三配位的 Cu 中心获得了足够的电子密度。
