Reactivity Studies of Thiophosgene and its Halo Versions towards Diazo Derivatives

The reactions of thiophosgene with diazo derivatives gives dichloro-alkene derivatives and cyclized, 1,2,3-thiadiazoles respectively. The product formation is mainly depending on substitutions on diazo substrates. When its halo versions, CSBr2 and in combination with bromide ion, CSBr2 less reactive than bromide ion with disubstituted diazo, give gem-dihalo derivatives whereas more reactive with mono substituted diazo to gives 1,2,3-thiadiazoles. In case CSI2 irrespective of substitution on diazo, iodide ion is more reactive then CSI2 was observed.

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.