(CO)4Re{trans-μ-HCC(CO2Me)}Re(CO)5 | 154965-96-5

• 英文名称: (CO)4Re{trans-μ-HCC(CO2Me)}Re(CO)5
• CAS: 154965-96-5
• 化学式: C₁₃H₄O₁₁Re₂
• 分子量: 708.582
• InChiKey: GWWBMTUKECPMIS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (CO)4Re{trans-μ-HCC(CO2Me)}Re(CO)5 以 正己烷 、 正庚烷 为溶剂， 生成
  参考文献：
  名称：

  Adams, Richard D.; Chen, Linfeng; Wu, Wengan, Organometallics, 1993, vol. 12, # 4, p. 1257 - 1265

  摘要：

  DOI：
• 作为产物：
  描述：

  以 正己烷 为溶剂， 以80%的产率得到(CO)4Re{trans-μ-HCC(CO2Me)}Re(CO)5
  参考文献：
  名称：

  Adams, Richard D.; Chen, Linfeng; Wu, Wengan, Organometallics, 1993, vol. 12, # 4, p. 1257 - 1265

  摘要：

  DOI：

文献信息

• Insertion of alkynes with electron-withdrawing substituents into a rhenium-rhenium bond. Evidence for an intramolecular insertion with a trans stereochemistry
  作者：Richard D. Adams、Linfeng Chen、Wengan Wu

  DOI：10.1021/om00059a010

  日期：1992.11

  The reaction of the dirhenium complex Re2-(CO)9(NCMe) (1) with electrophilic alkynes, R'C=CCO2R, proceeds by displacement of the NCMe ligand and addition of the alkyne with insertion Into the rhenium-rhenium bond to yield the dimetalated olefin complexes Re(CO)4-[trans-mu-R'C=C(CO2R)]Re(CO)5 (R = Me, R' = H (2a), Me (2b); R = Et, R' = C02Et (2c)) having a trans stereochemistry at the C-C double bond. The carboxylate group is coordinated to one of the rhenium atoms to form a metallacycle. Insensitivity to radical scavengers and the absence of crossover in a reaction of a mixture of labeled and unlabeled reagent indicate that the insertion of the alkyne into the metal-metal bond occurs by an intramolecular process. Crystal data for 2a: space group P2(1)/n, a = 6.644 (1) angstrom, b = 30.005 (8) angstrom, c = 18.036 (2) angstrom, beta = 96.09 (1)-degrees, Z = 8, 2468 reflections, R = 0.033.
• Rhenium complexes from alkynes. X-Ray crystal structures of Re2(μ-2η1,-C4Ph4) (CO)7 and Re{C,O-CH C[Re(CO)4(NMe3)]C(OMe)O}(CO)4
  作者：Michael I. Bruce、Paul J. Low、Brian W. Skelton、Allan H. White

  DOI：10.1016/0022-328x(94)87273-2

  日期：1994.1

  The molecular structure of Re-2(mu-2 eta(1),eta(4)-C(4)Ph(4))(CO)(7) obtained from Re-2(CO)(8)(NCMe), and C(2)Ph(2), consists of an Re-2(CO)(7) unit [Re-Re 2.874(1) Angstrom] bridged by a 2 eta(1),eta(4)-C(4)Ph(4) ligand, as proposed by earlier workers. Methyl propiolate is inserted into the Re-Re bond of Re-2(CO)(9)(NCMe), as shown by the molecular structure of the NMe(3) derivative of the product; the NMe(3) Ligand is attached to the non-chelated Re atom [Re-N 2.31(1) Angstrom].
• Facile alkyne coupling reactions in dirhenium carbonyl complexes
  作者：Richard D. Adams、Linfeng Chen、Wengan Wu

  DOI：10.1021/om00029a021

  日期：1993.5

  The complex (OC)4Re[trans-mu-HC=C(CO2Me)]Re(CO).5 (1) was converted to the reactive acetonitrile complex (OC)4Re[trans-mu-HC=C(CO2Me)]Re(CO)4(NCMe) (2) by reaction with Me3NO in acetonitrile. Under an atmosphere of CO, complex 2 reacts with HC=CCO2Me in refluxing CH2Cl2 to yield the new complexes (OC)4Re[mu-C(H)=C(CO2Me)C(H)=C(CO2Me)]-Re(CO)5 (3; 11 %) and (OC)4Re[C(H)=C(CO2Me)C(H)=C(CO2Me)C(H)=C(CO2Me)]Re(CO)4 (4a,b; 49 %, existing in solution as a mixture of isomers) by the head-to-tail coupling of two and three HC=CCO2Me molecules, respectively. In the absence of CO only compound 4 and a small amount of the new compound Re(CO)4[C6H2(CO2Me)(CO2Me)2] (5;6 %) were obtained. Complex 3 was converted into 4 by reaction with additional HC=CCO2Me in the presence of Me3NO. When heated to 98-degrees-C, 4 was transformed into 5 in 22 % yield. Three of the products, 3, 4a, and 5 were characterized crystallographically. In complex 3 the two linked HC=CCO2Me groups form a four-carbon chain between the metal-containing groups. One of the carboxylate substituents is also coordinated to form a five-membered metallacyclic ring. In complex 4a the metal-containing groups are joined by a six-carbon chain formed from the three alkynes, and two of the carboxylate groups are coordinated to form five- and six-membered metallacyclic rings. The six-carbon chain in 4 was transformed into a 2,4,6-tris(methoxycarbonyl)phenyl group that is a-coordinated to the metal atom and also has one of its carboxylate groups coordinated. Crystal data: for 3, space group P1BAR, a = 13.792(2) angstrom, b = 14.009(2) angstrom, c = 6.2734(6) angstrom, a = 91.47(1)-degrees, beta = 92.95(1)-degrees, gamma = 114.764(8)-degrees, Z = 2, 2120 reflections, R = 0.023; for 4a, space group P1BAR, a = 10.7738(8) angstrom, b = 13.179(2) angstrom, c = 9.024(1) angstrom, alpha = 96.52(1)-degrees, beta = 101.467(8)-degrees, gamma = 84.604(9)-degrees, Z = 2, 2428 reflections, R = 0.024; for 5, space group P1BAR, a = 9.947(1) angstrom, b = 11.840(2) angstrom, c = 7.977(1) angstrom, alpha = 106.99(1)-degrees, beta = 102.98(1)-degrees, gamma = 89.52(1)-degrees, Z = 2,1968 reflections, R = 0.022.