Preparation and Reaction of Some Di-<I>tert</I>-butylnitroxidopalladium(II) Complexes, PdX(Bu<I><SUP>t</SUP></I><SUB>2</SUB>NO)L (L=PPh<SUB>3</SUB>, AsPh<SUB>3</SUB>, P(OPh)<SUB>3</SUB>; X=C1, Br, I)
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概要
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PdX(Bu<I><SUP>t</SUP></I><SUB>2</SUB>NO)L (L=PPh<SUB>3</SUB>, AsPh<SUB>3</SUB>, P(OPh)<SUB>3</SUB>; X=Cl, Br, I) was isolated by the reactions of [PdCl(Bu<I><SUP>t</SUP></I><SUB>2</SUB>NO)]<SUB>2</SUB> with L and by the halogen exchange reactions of the chloro complexes with LiBr·H<SUB>2</SUB>O or NaI. PMR and IR spectra revealed that PdX(Bu<I><SUP>t</SUP></I><SUB>2</SUB>NO)(PPh<SUB>3</SUB>) and PdX(Bu<I><SUP>t</SUP></I><SUB>2</SUB>NO)(AsPh<SUB>3</SUB>) exist as only one geometrical isomer with the halogen atom <I>trans</I> to the oxygen atom of the nitroxide ligand, while two isomers of PdX(Bu<I><SUP>t</SUP></I><SUB>2</SUB>NO)[P(OPh)<SUB>3</SUB>] coexist in solution. The reaction of PdX(Bu<I><SUP>t</SUP></I><SUB>2</SUB>NO) (PPh<SUB>3</SUB>) (X=Cl, I) with triphenylphosphine was found to give Pd(PPh<SUB>3</SUB>)<SUB>4</SUB> together with Pd X<SUB>2</SUB>(PPh<SUB>3</SUB>)<SUB>2</SUB> and Bu<SUB>2</SUB>NO·. A similar reaction proceeded between PdCl(Bu<I><SUP>t</SUP></I><SUB>2</SUB>NO)[P(OPh)<SUB>3</SUB>] and triphenylphosphite to yield Pd[P(OPh)<SUB>3</SUB>]<SUB>3</SUB>, while a not well-defined complex [PdCl(AsPh<SUB>3</SUB>)<SUB>2</SUB>]<I><SUB>n</SUB></I> was obtained in the reaction of PdCl(Bu<I><SUP>t</SUP></I><SUB>2</SUB>NO)(AsPh<SUB>3</SUB>) with triphenylarsine.
- 公益社団法人 日本化学会の論文
著者
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Tanaka Toshio
Department Of Applied Physics Faculty Of Engineering Tokyo University
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Matsubayashi Gen-etsu
Department Of Applied Chemistry Faculty Of Engineering Osaka University
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Okunaka Masaaki
Department of Applied Chemistry, Faculty of Engineering, Osaka University
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