[PdI2(Me(2)dazdt)] is obtained from palladium powder via a 100% atom -economical Pd(0) leaching reaction using Me(2)dazdt (N,N'-dimethyl-perhydrodiazepine-2,3-dithione) and iodine. This complex is a versatile starting point for ligand exchange reactions with (di)phosphines, yielding trans-[PdI2(PPh3)(2)] and [PdI2(dppe)] (dppe = 1,2-bis-(diphenylphosphino)ethane). Further reaction with dithiocarbamates provides compounds of the form [Pd(DTC)(L)(n)](+) (DTC = dithiocarbamate; L = PPh3, n = 2; L = dppe, n = 1), which are highly active catalysts for regio- and chemoselective C H bond activation reactions. Using DTC ligands with trimethoxysilyl-terminated tethers, the palladium(II) units can be attached to the surface of core shell, silica -coated Fe3O4 nanoparticles. Once units form the catalytically active component of a recyclable, quasi -heterogeneous, Pd(II)-based catalytic system based on recovered palladium, illustrating the proposed circular model strategy. These investigations contribute to key steps in this process, such as efficient, atom-economical recovery, chemoselectivity of ligand substitution reactions, demonstration of catalytic activity, and the potential for immobilization of catalytic surface units derived from recovered metal.
From recovered palladium to molecular and nanoscale catalysts / Jantan, K. A.; Chan, K. W.; Melis, L.; White, A. J. P.; Marchio, L.; Deplano, P.; Serpe, A.; Wilton-Ely, J. D. E. T.. - In: ACS SUSTAINABLE CHEMISTRY & ENGINEERING. - ISSN 2168-0485. - 7:14(2019), pp. 12389-12398. [10.1021/acssuschemeng.9b01877]
From recovered palladium to molecular and nanoscale catalysts
Marchio L.Formal Analysis
;
2019-01-01
Abstract
[PdI2(Me(2)dazdt)] is obtained from palladium powder via a 100% atom -economical Pd(0) leaching reaction using Me(2)dazdt (N,N'-dimethyl-perhydrodiazepine-2,3-dithione) and iodine. This complex is a versatile starting point for ligand exchange reactions with (di)phosphines, yielding trans-[PdI2(PPh3)(2)] and [PdI2(dppe)] (dppe = 1,2-bis-(diphenylphosphino)ethane). Further reaction with dithiocarbamates provides compounds of the form [Pd(DTC)(L)(n)](+) (DTC = dithiocarbamate; L = PPh3, n = 2; L = dppe, n = 1), which are highly active catalysts for regio- and chemoselective C H bond activation reactions. Using DTC ligands with trimethoxysilyl-terminated tethers, the palladium(II) units can be attached to the surface of core shell, silica -coated Fe3O4 nanoparticles. Once units form the catalytically active component of a recyclable, quasi -heterogeneous, Pd(II)-based catalytic system based on recovered palladium, illustrating the proposed circular model strategy. These investigations contribute to key steps in this process, such as efficient, atom-economical recovery, chemoselectivity of ligand substitution reactions, demonstration of catalytic activity, and the potential for immobilization of catalytic surface units derived from recovered metal.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
