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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 32, Number 9
BKCSDE 32(9)
September 20, 2011 

Synthesis and Reactivity of Dinuclear Ni(II) Azido Complexes Containing Bithienylene or Terthienylene Bridging Ligands
Yong-Joo Kim*, Hyuck Hee Lee, Zhen Nu Zheng, Soon W. Lee
Azido, Thienylene, Trimethylsilyl isothiocyanate, Trimethylsilyl cyanide, Nickel
Dinuclear Ni(II)–thiophene halides, which contain linear bridging thienylenes, trans,trans-[(PR3)2(X)Ni–Y– Ni(X)(PR3)2] {X = Cl, Br; H2Y = 5,5'-dichloro-2,2'-bithiophene (H2bth); H2tth = 5,5''-dichloro-2,2':5',2''-terthiophene (H2tth)} were prepared by the oxidative addition of dihalobithiophene (H2bth) or dihaloterthiophene (H2tth) to [Ni(COD)2] in the presence of tertiary phosphines. Subsequent reactions of NaN3 with the dinuclear Ni(II)–thiophene chlorides gave the corresponding Ni(II)–azido complexes, trans,trans-[(PR3)2(N3)Ni–Y– Ni(N3)(PR3)2], whose reactivity toward trimethylsilyl pseudohalides such as trimethylsilyl isothiocyanates and cyanides was investigated. In addition, the reaction of trans-[BrNi(PEt3)2–C4H2S–C4H2S–CHO], a thienyl Ni(II) complex containing a terminal aldehyde group, with phosphonium ylide was examined.
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