Synthesis and Redox Behavior of Chalconido Clusters of Nickel, Palladium, and Platinum

• Project/Area Number: 03640526
• Research Category: Grant-in-Aid for General Scientific Research (C)
• Allocation Type: Single-year Grants
• Research Field: 無機・錯塩・放射化学
• Research Institution: Osaka City University
• Principal Investigator: MATSUMOTO Keiji Osaka City University, Faculty of Science, Associate professor, 理学部, 助教授 (50047164)
• Project Period (FY): 1991 – 1992
• Project Status: Completed (Fiscal Year 1992)
• Budget Amount: ¥1,700,000 (Direct Cost: ¥1,700,000); Fiscal Year 1992: ¥300,000 (Direct Cost: ¥300,000); Fiscal Year 1991: ¥1,400,000 (Direct Cost: ¥1,400,000)
• Keywords: Trinuclear cluster / Cyclic voltammetry / Sulfido ion / Selenido ion / Tellurido ion / Nickel / Palladium / Platinum / 3核錯体 / X線結晶構造 / サイクリックボルタムグラム

Research Abstract

Nine [M_3E_2(diphos)_3]^<2+> (M=Ni, Pd, Pt, E=S, Se, Te, diphos=1,2-bis(diphenylphosphino) ethane (dppe)) and six [M_3Se_2(diphos)_3]^<2+> (M=Ni, Pd, Pt, diphos=1,3-bis(diphenylphosphino)propane (dppp) or 1,4-bis(diphenylphosphino)butane (dppb)) clusters have been synthesized and X-ray structures of [Pt_3E_2(dppe)_3][BPh_4]_2 (E=Se, Te) were determined. The structures comprise three square-planar PtE_2P_2 coordination planes sharing two mu_3-E ligands. Cyclic voltammograms (CV) (20ﾟC or -18ﾟC) of [M_3E_2(dppe)_3]^<2+> (M=Ni, E=S, Se, Te) give two reversible couples which are one-electron process. CV's (20ﾟC or -18ﾟC) of [M_3E_2(dppe)_3]^<2+>one-electron process. CV's (20ﾟC OR -18ﾟC) of [M_3E_2(dppe)_3]^<2+> (M=Pd, Pt, E=S, Se, Te) except for (M=Pt, E=S) show one reversible couple which involves two-electron transfer. The ease of reduction follows the order Te>Se>S in these clusters [M_3E_2(dppe)_3]^<2+> (M=Ni, Pd, Pt).
The CV's of [M_3Se_2(dppe)_3]^<2+> (M=Ni, Pd, Pt) containing 5-membered chelate rings give reversible couples and that of [M_3Se_2(dppp)_3]^<2+> (M=Ni) (6-membered chelate ring) gives reversible couples, but those of [M_3Se_2(dppp)_3]^<2+> (M=Pd, Pt) are irreversible. The CV's of [M_3Se_2(dppp)_3]^<2+> (M=Ni, Pd, Pt) (7-membered chelate ring) are all irreversible. Reduction potentials of [M_3Se_2(dppb)_3]^<2+> (M=Ni, Pd, Pt) having 7-membered chelate rings are the highest and accordingly these are the easiest to reduce.

Research Products

• [Publications] Keiji Matsumoto: "Synthesis and Cyclic Voltammetry of Tri-nuclear Sulphido Clusters of Nickle(II),Palladium(II)and Platinum(II)and Selenido Clusters of Nickel(II)with 1,2-Bis(diphenylphosphino)ethane,and Crystal Structures of Sulphido and Selenido Clusters of Nickel(II)" J.Chem.Soc.,Dalton Trans.1265-1271 (1991)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Keiji Matsumoto: "Synthesis and Cyclic Voltammetry of Trinuclear Sulphido Clusters of Nickle(II), Palladium(II) and Platinum(II) and Selenido Clusters of Nickel(II) with 1,2-Bis(diphenylphosphino)-ethane, and Crystal Structures of Sulphido and Selenido Clusters of Nickel(II)" J. Chem. Soc., Dalton Trans.1265 (1991)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Keiji Matsumoto: "Synthesis and Cyclic Voltammetry of Trinuclear Sulphido Clusters of Nickle(II),Palladium(II)and Platinum(II) and Selenido Clusters of Nickel(II)with 1,2-Bis(diphenylphosphino)-ethane,and Crystal Structures of Sulphido and Selenido Clusters of Nickel(II)" J.Chem.Soc.,Dalton Trans.1265-1271 (1991)
• [Publications] 松本 圭司: "Synthesis and Cyclic Voltammetry of Trinuclear Sulphido Clusters of Nickel(II),Palladium(II),and Platinum(II) and Selenido Clusters of Nickel(II)with 1,2ーBis(diphenylphosphino)ethane,and Crystal Structures of Sulphido and Selenido Cluters of Nickel(II)" J.Chem.Soc.Dalton Trans.1265-1271 (1991)