| 157931-44-7

• CAS: 157931-44-7
• 化学式: C₅₃H₄₉OP₄Ru*Cl
• 分子量: 962.389
• InChiKey: XTIUNWWRNWWYJS-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  [RuHCl(CO)(PPh₃)₃] 在 C₂H₄(P(C₆H₅)2)2 作用下， 以 乙醇 为溶剂， 以72%的产率得到
  参考文献：
  名称：

  Synthesis of New Ruthenium(II) Carbonyl Hydrido, Alkenyl, and Alkynyl Complexes with Chelating Diphosphines

  摘要：

  Substitution of one or two triphenylphosphine ligands of Ru(CO)ClH(PPh(3))(3) by bidentate diphosphines Ph(2)P(CH2)(n)PPh(2) (L-L) (n = 1, dppm; n = 2, dppe; n = 3, dppp; n = 4, dppb) or 1, 1'-bis(diphenylphosphino)ferrocene (dppf) led to hydrides Ru(CO)ClH(PPh(3))(2)(L-L) or Ru(CO)ClH(PPh(3))(L-L). The hydride complexes were characterized spectroscopically and by one X-ray structure. Hydride Ru(CO)ClH(PPh(3))(dppf) crystallizes in the monoclinic space group P2(1)/n, with a 17.768(1) Angstrom, b = 25.252(2) Angstrom, c 11.213(1) Angstrom, beta = 92.83(1)degrees, Z = 4, and V = 4459.3(6) Angstrom(3). Reaction of Ru(CO)ClH(PPh(3))(3) or [Ru(CO)H(MeCN)(2)(PPh(3))(2)](PF6-)-P-+ with 2 equiv of diphosphines L-L led to [Ru(CO)H(L-L)(2)](+)A(-) (L-L = dppm, dppe, dppp) (A = Cl, PF6). Hydrides Ru(CO)ClH(PPh(3))(2)(L-L) react with 1-alkynes to give alkenyl complexes Ru(CO)Cl(CH=CHR)(PPh(3))(L-L) with a chelating diphosphine ligand. Ru(CO)ClH(PPh(3))(L-L) gave sigma-alkynyl complexes Ru(CO)Cl(C drop CR)L(L-L) directly in their reactions with 1-alkynes. The hydride with dppb as the ligand showed the highest reactivity. The preparation of hexaco ordinated alkenyl derivatives Ru(CO)Cl(CH=CHR)(PPh(3))(L-L) with a chelating diphosphine was carried out by treatment of other alkenyl derivatives with the diphosphines. Surprisingly, reaction of alkenyls Ru(CO)Cl(CH=CHR)(Me(2)Hpz)(PPh(3))(2) (R = CMe(3), p-MeC(6)H(4)) with dppf led to complexes Ru(CO)Cl(CH=CHR)(Me(2)Hpz)(dppf) by substitution of both PPh(3) ligands instead of the dimethylpyrazole. Ruthenium alkenyls Ru(CO)Cl(CH=CHR)L(dppf) (L = Me(2)Hpz, PPh(3)) react cleanly with 1-alkynes at room temperature to give alkynyl complexes Ru(CO)Cl(C drop CR)L(dppf) in good yield. This reaction was applied to the synthesis of a bimetallic complex Ru(CO)Cl(PPh(3))(dppf)(C drop C-p-C6H4C drop C)Ru(CO)Cl(PPh)(dppf) as a mixture of meso and dl diastereomers.

  DOI：

  10.1021/om00021a037