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

作者：Chang Xiaohong; Kim Mi Young; Kim Yong Joo^*; Huhc Hyun Sue; Lee Soon W

来源：Dalton Transactions, 2007, (7): 792-801.

DOI：10.1039/b616901e

Cyclopalladated tetranuclear Pd(II) complexes, [Pd-2(mu-Cl)(2)(Y)](2) (Y = L-1 or L-2; 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)(N-3) Pd - Y - Pd(N-3)(PR3)(2)] (Y= L-1 or L-2) or a cyclometallated complex [(PR3)(N-3) Pd - Y' - Pd(N-3)(PR3)] (Y' = C, N-L-2). Reactions of these Pd - azido complexes with CN - Ar (Ar = 2,6- Me2C6H3, 2,6-i-Pr2C6H3) or R - NCS ( R = i-Pr, Et, allyl) led to the complexes containing end-on carbodiimido groups [(PMe3)(2)(N=C=N - Ar) Pd - Y - Pd( N=C=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=C=N - Ar) Pd - Y' - Pd( N= C= N - Ar)(PMe3)] (Y' = C, N-L-1, C, N-L-2). We also report the preparation of linear, thienylene-bridged dinuclear Pd complexes [L-2(N-3) Pd - X(or X') - Pd(N-3) L-2] (L = PMe3 or PMe2Ph; H2X = 2,2'-bithiophene or H2X' = 2,2': 5', 2"-terthiophene) and their reactivity toward organic isocyanide and isothiocyanates.

• 出版日期2007
• 单位辽宁大学