イソシアニドを主たる配位子とする金属-金属結合を含む第10族金属錯体の電極合成
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概要
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Electrochemical preparations of the Group 10 metal isocyanide complexes containing metal-metal bonds are described. Electrochemical reductions of [MCl<SUB>2</SUB>(RNC)<SUB>2</SUB>] and [M(RNC)<SUB>2</SUB>(L<SUB>2</SUB>)]<SUP>2+</SUP> (M = Pd, Pt; L<SUB>2</SUB> = 2 RNC, 2 PPh<SUB>3</SUB>, Ph<SUB>2</SUB>P(CH<SUB>2</SUB>)<SUB>n</SUB>PPh<SUB>2</SUB>=diphos) were carried out at Pt and Hg electrodes and gave di- tri-, and high nuclear complexes, [M<SUB>2</SUB>Cl<SUB>2</SUB> (RNC)<SUB>4</SUB>], [M<SUB>2</SUB>(RNC)<SUB>4</SUB>L<SUB>2</SUB>]<SUP>2+</SUP>, [M<SUB>3</SUB>(RNC)<SUB>6</SUB>L<SUB>2</SUB>]<SUP>2+</SUP>, [HgPt<SUB>6</SUB>(RNC)<SUB>12</SUB>][HgPt<SUB>6</SUB>(RNC)<SUB>8</SUB>(diphos)<SUB>2</SUB>], [Hg<SUB>2</SUB>Pt<SUB>6</SUB>(RNC)<SUB>8</SUB>(diphos)<SUB>2</SUB>], and [Hg<SUB>2</SUB>Pt<SUB>6</SUB>(RNC)<SUB>6</SUB>(diphos)<SUB>3</SUB>], depending on the charge consumed and reduction potential. Electrochemistry of NiX<SUB>2</SUB>(RNC)<SUB>2</SUB> 8 at a Pt electrode is quasi-reversible, but the reaction at a Hg electrode proceeded with the CE mechanism; an initial chemical reaction of 8 with a Hg electrode occurred to give [{HgNi(RNC)<SUB>4</SUB>X<SUB>2</SUB>}<SUB>2</SUB>], and finally the redox reaction of the Hg complex was observed. Reactions of dimeric complexes with isocyanide, ML<SUB>2</SUB>(M=Ni, Pt), or ML<SUB>3</SUB>(M=Pd) fragments were carried out and the corresponding A-frame or linear trimetallic complexes were obtained.
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