cis,cis,trans-Ru(CO)(DMSO)(pyridine)2Cl2 | 166834-06-6

• 英文名称: cis,cis,trans-Ru(CO)(DMSO)(pyridine)2Cl2
• CAS: 166834-06-6
• 化学式: C₁₃H₁₆Cl₂N₂O₂RuS
• 分子量: 436.324
• InChiKey: YCUMYWNBTLERAA-UHFFFAOYSA-L

反应信息

• 作为产物：
  描述：

  吡啶 、 cis-dichloro-tris(dimethylsulfoxide)(carbonyl)ruthenium(II) 以 甲醇 为溶剂， 以45%的产率得到cis,cis,trans-Ru(CO)(DMSO)(pyridine)2Cl2
  参考文献：
  名称：

  Carbonyl Derivatives of Chloride-Dimethyl Sulfoxide-Ruthenium(II) Complexes: Synthesis, Structural Characterization, and Reactivity of Ru(CO)x(DMSO)4-xCl2 Complexes (x = 1-3)

  摘要：

  The reactivity of cis- and trans-RuCl2(DMSO)(4) with carbon monoxide has been thoroughly investigated. Depending on the choice of the solvent and the reaction conditions, cis-RuCl2(DMSO)(4) reacts with CO at ambient pressure replacing one, two or three DMSO molecules. The following derivatives have been isolated: trans,cis,cis-Ru-(CO)(DMSO)(DMSO)(2)Cl-2 (1), cis,cis,cis-Ru(CO)(2)(DMSO)(DMSO)Cl-2 (2), cis,trans,cis-Ru(CO)(2)(DMSO)(2)Cl-2 (3) and fac-Ru(CO)(3)(DMSO)Cl-2 (4). Compounds 1, 3 and 4 have been structurally characterized. 1 . 0.5H(2)O: monoclinic, P2(1)/c, Z = 8, a = 15.408(1) Angstrom, b = 15.398(2) Angstrom, c = 14.826(1) Angstrom, beta = 107.46(1)degrees. 3: orthorhombic, Pca2(1), Z = 8, a = 15.853(3) Angstrom, b = 11.380(2) Angstrom, c = 14.874(2) Angstrom. 4: orthorhombic, P2(1)2(1)2(1), Z = 4, a = 7.300(2) Angstrom, b = 9.297(2) Angstrom, c = 16.515(4) Angstrom, beta = 107.46(1)degrees. Reaction of trans-RuCl2(DMSO)(4) with CO at room temperature and ambient pressure leads to the replacement of either one or two DMSO ligands, depending on the reaction time, yielding trans,trans,trans-Ru(CO)(DMSO)(DMSO)(2)Cl-2 (5) and cis,cis,trans-Ru(CO)(2)(DMSO)(2)Cl-2 (6). The crystal structure of 5 has been determined. 5: monoclinic, P2(1), Z = 4, a = 7.417(3) Angstrom, b = 26.808(6) Angstrom, c = 8.368(4) Angstrom, beta = 107.55(7)degrees. Complex 3 is the thermodynamically most stable bis(carbonyl) species. Compounds 1-6 represent the first example of well-characterized Ru(II) chloride-DMSO-carbonyl complexes. Their most striking common feature is that coordination of carbon monoxide induces the selective isomerization of the DMSO trans to it from S- to O-bonding. Compounds 1-6 are versatile precursors for the synthesis of carbonylated Ru(II) species in which the DMSO ligands are partially or completely replaced by other ligands. Reaction of 1-6 with pyridine has been investigated and several products were isolated. The reactions were often accompanied by a geometrical isomerization. Complex 1 yields cis,cis,cis-Ru(CO)(py)-(DMSO)(2)Cl-2 (7), whose crystal structure has been determined. 7: triclinic, P $($) over bar$$ 1, Z = 2, a = 7.129(3) Angstrom, b = 7.918(2) Angstrom, c = 14.516(7) Angstrom, alpha = 84.70(3)degrees, beta = 88.14(3)degrees, gamma = 77.87(3)degrees. Complex 3 can replace either one DMSO ligand, forming the two geometrical isomers cis,cis,cis-Ru(CO)(2)(py)(DMSO)Cl-2 (8) and cis,trans,cis-Ru-(CO)(2)(py)(DMSO)Cl-2 (9), or two DMSO ligands, yielding cis,cis,trans-Ru(CO)(2)(py)(2)Cl-2 (10), where a cis to trans isomerization of the two chlorides occurred. Also the crystal structure of 9 has been determined; 9: triclinic, P $($) over bar$$ 1, Z = 4, a = 7.939(3) Angstrom, b = 12.863(5) Angstrom, c = 14.133(3) Angstrom, alpha = 105.95(2)degrees, beta = 95.10(2)degrees, gamma = 99.02(2)degrees. fac-Ru(CO)(3)(py)Cl-2 (11) was obtained from 4, while cis,cis,trans-Ru(CO)(DMSO)(py)(2)Cl-2 (12) and cis,cis,trans-Ru(CO)(2)(py)(2)Cl-2 (10) were synthesized from 5 and 6, respectively.

  DOI：

  10.1021/ic00123a004