Structural trends in a series of bulky dialkylbiarylphosphane complexes of CuI

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.

Hydroxycarbonylation of Alkenes with Formic Acid Using Rhodium Iodide complex and Alkylammonium Iodide

Hydroxycarbonylation of alkenes using formic acid (HCOOH) is ideal for the synthesis of various carboxylic acids as a means to develop a sustainable reaction system with lower environmental impact. In...