methylacetylene, dicobalt-hexacarbonyl complex | 41626-24-8

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: methylacetylene, dicobalt-hexacarbonyl complex
• 英文别名: Co2(CO)6(propyne)；Carbon monoxide;cobalt;prop-1-yne
• CAS: 41626-24-8
• 化学式: C₉H₄Co₂O₆
• 分子量: 326.114
• InChiKey: MXZWVPGPNKWRPJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.41
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methylacetylene, dicobalt-hexacarbonyl complex 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Labile SR′C(O)CRCH-bridged dicobalt complexes;synthesis structures 13CO labelling studies

  摘要：

  Three alkyne-bridged dicobalt carbonyl complexes, [Co-2(mu-RCCH)(CO)(6)] (R=H la, Me Ib, CH,OH Ic) have been reacted with Ph2P(SPh) and with the new thiophosphine ligands, Ph2P(SR') (R' = Bu-n, Bu-t), to give, initially, both mono-substituted [Co-2(mu-RCCH)(CO)(5){PPh2(SR')}] [(R' = Ph; R = H 2a, Me 2b, CH2OH 2c), (R' = Bu-n; R= H 3a, Me 3b, CH2OH 3c), (R' = Bu-t; R= H 4a, Me 4b)] and bis-substituted [Co-2(mu-RCCH)(CO)(4){ PPh2(SPh)}(2)] [(R' = Ph; R = H 5a, Me 5b, CH2OH 5c), (R' = Bu-n; R = H 6a, Me 6b, CH2OH 6c), (R'=Bu-t; R=H 7a, Me 7b)] products. Thermolysis of complexes 2-4 gives [Co-2(mu-PPh2){mu-SR'C(O) CRCH}(CO)(4)] [(R' = Ph; R = H 8a, Me 8b, CH2OH Sc), (R' = Bu-n; R = H 9a, Me 9b), (R' = Bu-t; R= H 10a, R= Me 10b)] in which sulphur-phosphorus bond cleavage and sulphur-carbon bond formation at the dicobalt centre have occurred to generate SR'C(O)CRCH ligands incorporated into 5-membered ring metallacycles. The transformations are regiospecific with the bulky substituents (R = H) in all cases being located adjacent to the CO moiety of the metallacycle. Treatment of the complex [Co-2(mu-PPh2){mu-SPhC(O)CHCH}(CO)(4)] 8a with (CO)-C-13 and monitoring of the reaction via C-13-{H-1}-NMR spectroscopy reveals the formation of a selectively labelled species, [Co-2(mu-PPh2){mu-(SPhC)-C-13(O)CHCH}((CO)-C-13)(2)(CO)(2)], in which the ketonic bridging carbonyl signal has been enhanced, while only two of the four signals due to the terminal carbonyl groups have been similarly enhanced. The mechanistic implications of this labelling study are discussed and pathways postulated for the reversible fragmentation of the SR'C(O)CRCH-bridged dicobalt systems. Single crystal X-ray diffraction studies have been performed on [Co-2(mu-HCCH)(CO)(4){PPh2(SBun)}(2)] 6a, revealing axially substituted thiophosphine groups and on [Co-2(mu-PPh2){mu-sBu(n)C(O)CHCH}(CO)(4)] 9a, in which an almost planar Co-S-C-C=C metallacycle-coordinated to the other cobalt is observed. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(98)00103-x
• 作为产物：
  描述：

  bromomethylidynetricobalt nonacarbonyl 在 C₂H₅OH 、 H₂SO₄ 、 H₂O 、 CH₃OH 、 (C₂H₅CO)2O 、 HPF₆ 作用下， 以 正己烷 、 硫酸 、 水 为溶剂， 生成 methylacetylene, dicobalt-hexacarbonyl complex
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Co: Org.Verb.2, 3.1.3.5, page 152 - 167

  摘要：

  DOI：

文献信息

• Acetylenic derivatives of metal carbonyls I. Substitution reactions of CO2(CO)6C2RR′ complexes
  作者：G. Cetini、O. Gambino、R. Rossetti、E. Sappa

  DOI：10.1016/s0022-328x(00)84714-2

  日期：1967.4

  In this work the substitution reactions were studied, of one acetylenic derivative, by another, in the complexes Co2(CO)6C2RR′ in which R and R′CF3, COOCH3, C6H5, CH2Cl, CH3, CH2N(C2H5)2 and H.

  在这项工作中的取代反应进行了研究，一个炔属衍生物的，通过另一个，在钴络合物2（CO）6 c ^ 2 RR'，其中R和R'CF 3，COOCH 3，C 6 H ^ 5，CH 2 Cl，CH 3，CH 2 N（C 2 H 5）2和H。
• Reactions of diarsines with bi- and tri-metallic carbonyl complexes containing cobalt
  作者：Nick Choi、Gráinne Conole、Jason D. King、Martin J. Mays、Mary McPartlin、Caroline L. Stone

  DOI：10.1039/a906611j

  日期：——

  Reaction of the diarsines As2R4 (R = Me or Ph) with alkyne-bridged dicobalt hexacarbonyl complexes leads to products with bridging (AsR2)2O ligands and to the production of simple AsR3 substituted complexes; alkylidyne tricobalt nonacarbonyl complexes exhibit parallel reactivity with As2R4. Thermolysis of the complex [Co2(μ-PhCCPh)μ-(AsMe2)2O}(CO)4] gives the tetra-substituted complex, [Co2(μ-PhCCPh)μ-(AsMe2)2O}2(CO)2]. Reaction of the heterometallic complex [(OC)3Coμ-C2(CO2Me)2}MoCp(CO)2] with As2Ph4 affords [(HO)Ph2As}(OC)2Coμ-C2(CO2Me)2}MoCp(CO)2], supporting the suggestion of a possible hydrolytic mechanism for the formation of the (AsR2)2O bridged complexes.

  二砷化物As2R4（R = Me或Ph）与炔桥联二钴六羰基配合物的反应产生了具有桥联(AsR2)2O配体的产物，以及生成简单的AsR3取代配合物；烷基亚砜三钴壬羰基配合物表现出平行的反应性。复杂配合物[Co2(μ-PhCCPh)μ-(AsMe2)2O}(CO)4]的热分解产生了四取代配合物，[Co2(μ-PhCCPh)μ-(AsMe2)2O}2(CO)2]。异金属配合物[(OC)3Coμ-C2(CO2Me)2}MoCP(CO)2]与As2Ph4反应生成[(HO)Ph2As}(OC)2Coμ-C2(CO2Me)2}MoCP(CO)2]，支持了(AsR2)2O桥联配合物形成的可能水解机制的建议。
• New organoarsino-bridged cobalt carbonyl complexes derived from reactions of [Co2(CO)8] or [Co2(μ-alkyne)(CO)6] with cyclo-(AsPh)6
  作者：Rohini M. De Silva、Martin J. Mays、John E. Davies、Paul R. Raithby、Moira A. Rennie、Gregory P. Shield

  DOI：10.1039/a706576k

  日期：——

  rsane (PhAs)6 with [Co2(CO)8] in toluene at ambient temperature resulted in As–As bond cleavage and the new complexes [Co4(µ4-AsPh)2(CO)10] 1 and [Co4(µ3-AsPh)(µ4-η2∶η2∶η1-As4Ph4)(CO)10] 2. In contrast, reaction of cyclo-(PhAs)6 with the alkyene-bridged complexes [Co2(µ-R1CCR2)(CO)6] in toluene or in benzene at 65 °C afforded the new complexes [Co2(µ-R1CCR2)µ-cyclo-(PhAs)6}(CO)4] (R1 = R2 = H 3; or

  室温下，六苯基环六砷烷（PhAs）6与[Co 2（CO）8 ]在甲苯中的反应导致As-As键断裂，以及新的配合物[Co 4（µ 4 -AsPh）2（CO）10 ] 1和[共4（μ 3 -AsPh）（μ 4 -η 2 :η 2 :η 1 -As 4博士4）（CO）10 ] 2。相比之下，反应环- （PHAS）6与alkyene桥连络合物[Co 2（µ-R 1 C CR2）（CO） 6 ]在甲苯中或在65°C的苯中提供了新的络合物[Co 2（µ-R 1 CCR 2）µ-环-（PhAs） 6 }（CO） 4 ]（R 1  = R 2  = H 3;或Ph 4和5（异构体）; R 1  = Ph，R 2  = H 6; R 1  = Me，R 2  = H 7）其中As 6戒指仍然完好无损。所有七个产品均已通过光谱表征，此外，化合物1-4已通过X射线衍射分析进行了结构表征。1的分子结构包括一个矩
• Synthesis of [Co₂(µ-PPh₂C₃H₄)(µ-PPh₂)(CO)₄]; its reactions with P(OMe)₃and with alkynes
  作者：Andrew J. M. Caffyn、Martin J. Mays、Gregory A. Solan、Gráinne Conole、Antonio Tiripicchio

  DOI：10.1039/dt9930002345

  日期：——

  The bis(phosphido)-bridged complex [Co2(µ-PPh2)2(CO)6]1 undergoes an insertion reaction of allene into one of the phosphido bridges, to give the new ligand-bridged dinuclear cobalt complex [Co2(µ-PPh2C3H4)(µ-PPh2(CO)4]2 in high yield. Complex 2 reacts with P(OMe)3 to give the monosubstituted derivative [Co2(µ-PPh2C3H4)(µ-PPh2)(CO)3P(OMe)3}]3 in which substitution has occurred at the allyl-co-ordinated

  双（磷基）桥连的配合物[Co 2（µ-PPh 2）2（CO）6 ] 1经历了异戊二烯插入一个磷桥中的插入反应，得到了新的配体桥连的双核钴配合物[Co 2（µ-PPh 2 C 3 H 4）（µ-PPh 2（CO）4 ] 2高收率。络合物2与P（OMe）3反应生成单取代衍生物[Co 2（µ-PPh 2 C 3 H 4）（µ-PPh 2）（CO）3P（OMe）3 }] 3，其中取代发生在烯丙基配位的钴原子上。配合物2还与炔烃RC CH（R CH 2 OH，Me或H）反应，该炔烃与CO分子一起插入剩余的磷桥中，从而生成[CO 2（µ-PPh 2 C 3 H 4）µ -PPh 2 C（O）CHCR}（CO）3 ]（R = CH 2 OH 4a，Me 4b或H 4c）。在MeC CH得到4b的情况下，第二种异构体[Co 2（µ-PPh 2 C3 ħ 4）μ-PPH 2 C（O）CMeCH}（CO）
• The reactivity of acetylenes coordinated to cobalt
  作者：Gyula Váradi、István T. Horváth、Gyula Pályi、László Markó、Yurii L. Slovokhotov、Yurii T. Struchkov

  DOI：10.1016/s0022-328x(00)93470-3

  日期：1981.2

  The “lactone” complexes, (C4O2R1,R2)Co2(CO)7, [μ2-carbonyl)[μ2-spiro-(2,3-substituted-2-butene-4-olide-4-ylidene)] [bis(tricarbonyl-cobalt)(CoCo) derivatives, were found to react with acetylenes (R3C2R4. This reaction yields the known acetylene complexes (R3C2R4Co2(CO)6 and two isomeric compounds with the composition [(C4O2R1,R2)(R3C2R4)2]Co2(CO)5. Spectroscopic arguments and X-ray structure determination

  所述“内酯”配合物，（C 4 Ò 2 - [R 1，R 2）有限公司2（CO）7，[μ 2羰基）[μ 2 -螺（2,3-取代-2-丁烯-4-内酯发现四（亚丙基）] [双（三羰基-钴）（CoCo）衍生物与乙炔（R 3 C 2 R 4）反应，该反应生成已知的乙炔配合物（R 3 C 2 R 4 Co 2（CO）6和两种异构体化合物，其组成为[（C 4 O 2 R 1，R 2）（R 3 C 2 R 4）2 ] Co 2（CO）5。光谱参数和X射线结构测定表明，两种异构体包含σ，π-C 5个配位体结合到二者Co原子。确定了这些异构体的结构。