930766-45-3Relevant academic research and scientific papers
Dinuclear palladium-azido complexes containing thiophene derivatives: Reactivity toward organic isocyanides and isothiocyanates
Chang, Xiaohong,Kim, Mi-Young,Kim, Yong-Joo,Huh, Hyun Sue,Lee, Soon W.
, p. 792 - 801 (2008/02/05)
Cyclopalladated tetranuclear Pd(ii) complexes, [Pd2(-Cl) 2(Y)]2 (Y = L1 or L2; H 2L1 = di(2-pyridyl)-2,2′-bithiophene; H 2L2 = 5,5″-di(2-pyridyl)-2,2′:5′, 2″-terthiophene), containing two pyridyl-α, α′- disubstituted derivatives of thiophene were prepared. Treating these products with PR3 and subsequently with NaN3 produced the dinuclear Pd-azido complexes [(PR3)2(N3)Pd-Y-Pd(N 3)(PR3)2] (Y = L1 or L2) or a cyclometallated complex [(PR3)(N3)Pd-Y′- Pd(N3)(PR3)] (Y′ = C,N-L2). Reactions of these Pd-azido complexes with CN-Ar (Ar = 2,6-Me2C6H 3, 2,6-i-Pr2C6H3) or R-NCS (R = i-Pr, Et, allyl) led to the complexes containing end-on carbodiimido groups [(PMe3)2(NCN-Ar)Pd-Y-Pd(NCN-Ar)(PMe3) 2] or S-coordinated tetrazole-thiolato groups {(PMe3) 2[CN4(R)]S-Pd-Y-Pd-S[CN4)(R)](PMe 3)2}. Interestingly, when treated with elemental sulfur, the carbodiimido complexes transformed into the cyclometallated derivatives, [(PMe3)(NCN-Ar)Pd-Y′-Pd(NCN-Ar)(PMe3)] (Y′ = C,N-L1, C,N-L2). We also report the preparation of linear, thienylene-bridged dinuclear Pd complexes [L2(N3)Pd-X(or X′)-Pd(N3)L2] (L = PMe3 or PMe 2Ph; H2X = 2,2′-bithiophene or H2X′ = 2,2′:5′,2″-terthiophene) and their reactivity toward organic isocyanide and isothiocyanates. The Royal Society of Chemistry.
