Dinuclear palladium–azido complexes containing thiophene derivatives: reactivity toward organic isocyanides and isothiocyanates

Cyclopalladated tetranuclear Pd(II) complexes, [Pd2(micro-Cl)2(Y)]2 (Y = L1 or L2; H2L1 = di(2-pyridyl)-2,2'-bithiophene; H2L2 = 5,5''-di(2-pyridyl)-2,2':5',2''-terthiophene), containing two pyridyl-alpha, alpha'-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(N3)(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-Me(2)C(6)H(3), 2,6-i-Pr(2)C(6)H(3)) or R-NCS (R = i-Pr, Et, allyl) led to the complexes containing end-on carbodiimido groups [(PMe3)2(N[double bond]C[double bond]N-Ar)Pd-Y-Pd(N[double bond]C[double bond]N-Ar)(PMe3)2] or S-coordinated tetrazole-thiolato groups {(PMe3)2[CN4(R)]S-Pd-Y-Pd-S[CN4)(R)](PMe3)2}. Interestingly, when treated with elemental sulfur, the carbodiimido complexes transformed into the cyclometallated derivatives, [(PMe3)(N[double bond]C[double bond]N-Ar)Pd-Y'-Pd(N[double bond]C[double bond]N-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 PMe2Ph; H2X = 2,2'-bithiophene or H2X' = 2,2':5',2''-terthiophene) and their reactivity toward organic isocyanide and isothiocyanates.