• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3239-3244
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• 2011

Dinuclear Ni(II)-thiophene halides, which contain linear bridging thienylenes, trans,trans-[$(PR_3)_2$(X)Ni-Y-Ni(X)$(PR_3)_2$] {X = Cl, Br; $H_2Y$ = 5,5'-dichloro-2,2'-bithiophene ($H_2bth$); $H_2tth$ = 5,5"-dichloro-2,2':5',2''-terthiophene ($H_2tth$)} were prepared by the oxidative addition of dihalobithiophene ($H_2bth$) or dihaloterthiophene ($H_2tth$) to [$Ni(COD)_2$] in the presence of tertiary phosphines. Subsequent reactions of $NaN_3$ with the dinuclear Ni(II)-thiophene chlorides gave the corresponding Ni(II)-azido complexes, trans,trans-[$(PR_3)_2(N_3)$Ni-Y-Ni$(N_3)(PR_3)_2$], whose reactivity toward trimethylsilyl pseudohalides such as trimethylsilyl isothiocyanates and cyanides was investigated. In addition, the reaction of trans-[$BrNi(PEt_3)_2-C_4H_2S-C_4H_2S$-CHO], a thienyl Ni(II) complex containing a terminal aldehyde group, with phosphonium ylide was examined.