[(PPh3)2N][Ru(CO)2Cl3(η(1)-OCHN(CH3)2)] | 192769-75-8

• 英文名称: [(PPh3)2N][Ru(CO)2Cl3(η(1)-OCHN(CH3)2)]
• CAS: 192769-75-8
• 化学式: C₅H₇Cl₃NO₃Ru*C₃₆H₃₀NP₂
• 分子量: 875.133
• InChiKey: RBHHXSNXVHFTLP-UHFFFAOYSA-K

反应信息

• 作为产物：
  描述：

  [PPN][RuCl₃(CO)₃] 、 N,N-二甲基甲酰胺 以 N,N-二甲基甲酰胺 为溶剂， 以57%的产率得到[(PPh3)2N][Ru(CO)2Cl3(η(1)-OCHN(CH3)2)]
  参考文献：
  名称：

  Promoter Effect of Chloride Ions on the Ruthenium-Catalyzed Hydroesterification of Ethylene with Methyl Formate. Design and Evaluation of New Poly- and Mononuclear Catalyst Precursors

  摘要：

  The catalytic hydroesterification of ethylene with methyl formate to produce methyl propionate is shown to take place in the presence of trinuclear ruthenium carbonyl complexes modified by anionic nucleophiles such as amido (anilinopyridyl), alkoxy (pyridonate), or halide ligands, regarded as potential promoters. The best results (100% conversion, 99% selectivity) are obtained with the mixture Ru-3(CO)(12) + [PPN]Cl(1/1) under the following experimental conditions: [HCOOMe]/[cat.] = 345, DMF solvent, P(C2H4) = 20 atm (at 25 degrees C), T = 160 degrees C, time 12 h. The complex [PPN][Ru-3(mu(3)-Cl)(CO)(9)] (3) resulting from the addition of [PPN]Cl to Ru-3(CO)(12) reacts cleanly with an excess of [PPN]Cl in refluxing THF under a stream of inert gas to produce the unique dianionic species [PPN](2)[Ru-4(mu-Cl)(2)(CO)(11)] (4) (70% yield). The X-ray structure analysis of 4 is reported (triclinic P1, No. 2, a 18.209(2) Angstrom, b = 18.877(3) Angstrom, c = 13.895(2) Angstrom, a = 110.70(1)degrees, beta = 108.43(1)degrees, gamma = 87.43(1)degrees, V = 4226(1) Angstrom(3), Z = 2, R = 0.053, R(w) = 0.069). The dianionic tetranuclear unit of 4 consists of a basic triangular metal framework ''Ru-3(CO)(9)'' one face of which is supported by a spiked ''Ru(CO)(2)Cl-2'' fragment involving a 16e metal center exhibiting a square pyramidal geometry. Extended Huckel MO calculations indicate a large HOMO/LUMO gap (1.45 eV). Facile loss of Cl- from the above dianion is induced by capture of CO, leading to the known butterfly complex [PPN][Ru-4(mu-Cl)(CO)(13)] (5). Complex 4 also reacts with O-2 at 25 degrees C to provide the new oxo derivative [PPN](2)[RU(4)(mu(4)-O)(mu-Cl)(4)(CO)(10)] (6) The structure of 6 has been determined by X-ray diffraction (triclinic P1, No. 2, a = 13.226(5) Angstrom, b = 25.533(2) Angstrom, c = 12.771(3) Angstrom, a = 92.39(1)degrees, beta 114.77(3)degrees, gamma = 85.92(2)degrees, V = 3906(2) Angstrom(3), Z = 2, R = 0.038, R(w) = 0.045). Its dianionic unit consists of a distorted quadratic antiprism based on two rectangular faces RU(mu-Cl)(2)RU and containing an encapsulated oxygen atom linked to the four ruthenium centers. The anionic complexes 4-6 also act as catalyst precursors for the hydroesterification reaction. Analysis of the solutions recovered at the end of all catalytic runs indicate the presence of [PPN](2)[Ru-6(C)(CO)(16)] as the principal metal-containing derivative. The probable mononuclear nature of the active species is suggested. A detailed investigation of the catalytic system based on [PPN][Ru(CO)(3)Cl-3] (7) (prepared here in 81% yield by a new one-pot procedure) is reported. The results show that catalysis in the presence of the latter complex takes place readily without an induction period. Furthermore, a comparative evaluation of the four salts 7, [PPN][Ru(CO)(3)I-3] (8), [PPN][Ru(CO)(3)Cl2I] (9), and [PPN][Ru(CO)(3-)CII2] (10) as catalyst precursors reveals that chloride is a better promoter than iodide under the experimental conditions defined above, using DMF (or related amides) as solvent. Catalysis in the presence of 7 (and 3 equiv of NEt(3) as cocatalyst) is complete within 2 h (100% conversion and 99% selectivity; overall turnover frequency 170 h(-1), corresponding to an initial activity of the order of 700 h(-1)).Complex 7 is seen to react readily with DMF at 160 degrees C within 30 min to produce the new complex [PPN][Ru(CO)(2)Cl-3(eta(1)-DMF)] (11), isolated in 60% yield. The X-ray structure of 11 is reported (monoclinic P2(1)/c, a = 9.000(2) Angstrom, b = 21.176(2) Angstrom, c = 21.080(1) Angstrom, beta = 93.89(8)degrees, V = 4008.3(9) Angstrom(3), Z = 4, R = 0.028, R(w) = 0.030). The three chloride ligands adopt a meridional arrangement, whereas the DMF ligand, bound via its oxygen atom, occupies one of the two apical sites.

  DOI：

  10.1021/om00004a027