methylidynetricobalt(I)nonacarbonyl

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: methylidynetricobalt(I)nonacarbonyl
• 英文别名: μ-ethylidene-nona(carbonyl)-tri(cobalt)；methylidynetricobalt nanocarbonyl；ethylidyne tricobalt nonacarbonyl
• 化学式: C₁₁H₃Co₃O₉
• 分子量: 456.119
• InChiKey: KKHPMWJWWUDZES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 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：

  methylidynetricobalt(I)nonacarbonyl 在 I₂ 作用下， 以 乙醚 为溶剂， 生成 1,1,1-三碘乙烷
  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：
• 作为产物：
  描述：

  (acetylene)hexacarbonyldicobalt 以 not given 为溶剂， 以49%的产率得到methylidynetricobalt(I)nonacarbonyl
  参考文献：
  名称：

  The Association of an Acetylene with Three Metal Atoms; A New Trinuclear Cobalt Complex

  摘要：

  DOI：

  10.1021/ja01557a018

文献信息

• Chemistry of methinyltricobalt enneacarbonyls. Part V. Tertiary phosphine and arsine derivatives
  作者：T. W. Matheson、B. H. Robinson、W. S. Tham

  DOI：10.1039/j19710001457

  日期：——

  Mono-, di-, and tri-substituted tertiary phosphine and arsine derivatives of methinyltricobalt enneacarbonyls have been prepared. The co-ordination behaviour of the cluster is determined by the apical substituent Y, and the stereochemistry adopted is one which minimizes nonbonded carbonyl interactions. Thus the majority of mono-substituted complexes have the same structure as MeCCo3(CO)8Ph3P but other

  已经制备了甲基三甲基叔丁基烯基羰基的单，二和三取代的叔膦和砷化氢衍生物。团簇的配位行为由顶端取代基Y决定，采用的立体化学是使非键合羰基相互作用最小化的一种。因此，大多数单取代的配合物具有与MeCCo 3（CO）8 Ph 3 P相同的结构，但其他MeCCo 3（CO）8 L化合物采用羰基桥联构型。二取代和三取代的配合物也具有桥联结构。已经确定了溶液中不同类型的结构异构现象。
• 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。
• Phosphorus–oxygen bond formation on organo-capped tricobalt centres via phosphorus–hydrogen or phosphorus–phosphorus bond scission
  作者：Gillian A. Acum、Martin J. Mays、Paul R. Raithby、Harold R. Powell、Gregory A. Solan

  DOI：10.1039/a702669b

  日期：——

  Chromatographic work-up of the initial products of the reaction of the secondary phosphine PPh2H with [Co3(µ3-CR)(CO)9] (R = Me 1a or CO2Me 1b) at 308 K in heptane gave the mono- and bis-substituted complexes [Co3(µ3-CR)(CO)8(PPh2H)] (R = Me 2a or CO2Me 2b) and [Co3(µ3-CR)(CO)7(PPh2H)2] (R  Me 3a or CO2Me 3b) and, in addition, when R = Me, the complex [Co3(µ3-CMe)(µ-Ph2POPPh2)(CO)6(PPh2H)] 4a, in which phosphorus–oxygen bond formation has occurred. Thermolysis of complex 2a at 343 K in heptane gave 1a and [Co3(µ3-CMe)(µ-H)(µ-PPh2)(CO)7] 5a, while thermolysis of 3a under the same conditions afforded 4a, a trace of 5a and [Co3(µ3-CMe)(µ-H)(µ-PPh2)(CO)6(PPh2H)] 6a. Similar reactions with the µ3-CCO2Me capped species 2b and 3b resulted in unstable non-isolable species. Treatment of complexes 3a, 3b with CO at 343 K causes the replacement of first one and then the other PPh2H ligand by CO to give 2a, 2b and then 1a, 1b respectively, while reformation of a phosphorus–hydrogen bond to give initially 2a or 3a can be achieved on carbonylation of either complex 5a or 6a. Substitution of a PPh2H group in 4a can be achieved by purging with CO to give [Co3(µ3-CMe)(µ-Ph2POPPh2)(CO)7] 7a. Complex 7a can also be prepared directly by the reaction of 1a with the diphosphane P2Ph4 as can the analogue [Co3(µ3-CCO2Me)(µ-Ph2POPPh2)(CO)7] 7b on reaction of 1b. The intermediates [Co3(µ3-CR)(CO)8(P2Ph4)] (R = Me 8a or CO2Me 8b) and [Co3(µ3-CR)(µ-P2Ph4)(CO)7] (R = Me 9a or CO2Me 9b) isolated in the reactions can be converted under the same reaction conditions into 7a and 7b respectively. Complex [Co3(µ3-CMe)(µ-Ph2POPPh2)(CO)6(PPhMe2)] 4a′, the tertiary phosphine analogue of 4a, has been prepared from the reaction of 7a with PPhMe2. The structures of complexes 4a′ and 5a have been determined by single crystal X-ray diffraction studies.

  在308 K的庚烷中，二次膦PPh2H与[Co3(µ3-CR)(CO)9]（R = Me 1a或CO2Me 1b）反应的初始产物经色谱处理后得到单取代和双取代的配合物[Co3(µ3-CR)(CO)8(PPh2H)]（R = Me 2a或CO2Me 2b）和[Co3(µ3-CR)(CO)7(PPh2H)2]（R = Me 3a或CO2Me 3b），此外，当R = Me时，还得到了配合物[Co3(µ3-CMe)(µ-Ph2POPPh2)(CO)6(PPh2H)] 4a，其中发生了磷-氧键的形成。在343 K的庚烷中热分解配合物2a得到了1a和[Co3(µ3-CMe)(µ-H)(µ-PPh2)(CO)7] 5a，而相同条件下热分解3a得到了4a、少量的5a和[Co3(µ3-CMe)(µ-H)(µ-PPh2)(CO)6(PPh2H)] 6a。与µ3-CCO2Me封端的物种2b和3b类似的反应产生了不稳定的非可分离物种。在343 K下用CO处理配合物3a, 3b会导致PPh2H配体被CO逐步替换，分别先得到2a, 2b，然后得到1a, 1b，而在配合物5a或6a的羰基化过程中可以重新形成磷-氢键，最初得到2a或3a。通过用CO吹扫可以实现4a中PPh2H基团的取代，得到[Co3(µ3-CMe)(µ-Ph2POPPh2)(CO)7] 7a。配合物7a也可以通过1a与二膦P2Ph4的反应直接制备，类似地，通过1b的反应可以制备出相似的[Co3(µ3-CCO2Me)(µ-Ph2POPPh2)(CO)7] 7b。在反应中分离得到的中间体[Co3(µ3-CR)(CO)8(P2Ph4)]（R = Me 8a或CO2Me 8b）和[Co3(µ3-CR)(µ-P2Ph4)(CO)7]（R = Me 9a或CO2Me 9b）可以在相同的反应条件下分别转化为7a和7b。通过7a与PPhMe2的反应，已经制备出了配合物[Co3(µ3-CMe)(µ-Ph2POPPh2)(CO)6(PPhMe2)] 4a′，即4a的三级膦类似物。通过单晶X射线衍射研究，已经确定了配合物4a′和5a的结构。
• Studies of metal exchange reactions: the synthesis and structures of heteronuclear metal clusters containing the indenyl ligand (μ3-CR)Co2M(CO)8(η5- Ind)(R=H,CH3,C6H5,COOC2H5; M=Mo,W)
  作者：Wei-Qiang Zhang、Bao-Hua Zhu、Bin Hu、Yu-Hua Zhang、Quan-Yi Zhao、Yuan-Qi Yin、Jie Sun

  DOI：10.1016/j.jorganchem.2003.11.028

  日期：2004.2

  The novel tetrahedral clusters (μ3-CR)Co2M(CO)8(η5-Ind) (M=Mo,W; R=H, CH3, C6H5, COOC2H5) 5–12 containing the indenyl ligand were isolated from reactions of tricobalt clusters (μ3-CR)Co3(CO)9 (R=H, CH3, C6H5, COOC2H5) and K(η5-Ind)M(CO)3 (M=Mo,W) under mild conditions. The cluster complex (μ3-CC6H5)CoMo2(CO)7(η5-Ind)(η5-Cp (Cp*=C5H4C(O)CH3) 16 was obtained via the stepwise metal exchange reaction of

  新颖的四面体簇（μ 3 -CR）有限公司2 M（CO）8（η 5 -Ind）（M =钼，钨; R = H，CH 3，C 6 H ^ 5，COOC 2 H ^ 5）5 - 12含茚基配位体是从（μ三钴簇的反应中分离3 -CR）有限公司3（CO）9（R = H，CH 3，C 6 H ^ 5，COOC 2 H ^ 5）和K（η 5 -Ind）M （CO）3（M = Mo，W）在温和条件下。簇络合物（μ 3 -CC 6 ħ 5）的CoMo 2（CO）7（η 5 -Ind）（η 5 -Cp（CP * = C 5 H ^ 4（O）CH 2 C 6 3）16经由逐步得到络合物（μ的金属交换反应3 -CC 6 ħ 5）有限2的Mo（CO）8（η 5 -Ind）9用Na（η 5 -CpMo（CO）3，但其中反应（μ 3 -CC 6高5）有限公司2的Mo（CO）8（η 5 -Cp *）15与K（η 5 -In
• Formation of novel chelating phosphine ligands via the reaction of [WCC₆H₄Me-4(CO)₂(η-C₅H₅)] with the bidentate phosphine C₆H₄(PH₂)₂-1,2; X-ray crystal structures of the complexes [W{σ,η³-C₆H₄(PH₂)(PC{OH}CH{C₆H₄Me-4})-1,2}(CO)(η-C₅H₅)], [{Wl{C₆H₄(PH₂)(P{Me}C{O}CH₂{C₆H₄Me-4})-1,2}(CO)(η-C₅H₅)·(]1/2C₄H₈O), and [WCo₃(µ₃-CR){µ-C₆H₄(PH₂)(PC{OH}CH{C₆H₄Me-4})-1,2}(CO)₉(η-C₅H₅)](R = H or Me)
  作者：James E. Denison、John C. Jeffery、Suanna Harvey、Peter Müller、K. D. Vinindra Weerasuria

  DOI：10.1039/c39900001023

  日期：——

  Treatment of the mononuclear alkylidyne complex [WCC6H4Me-4(CO)2(η-C5H5)] with one equivalent of the bidentate phosphine C6H4(PH2)2–1,2 affords the metalla-phosphine complex [Wσ,η3-C6H4(PH2)(PCOH}CHC6H4Me-4})-1,2}(CO)(η-C5H5)] which has an unused lone pair of electrons on the central phosphorus atom of the chelate ring and which undergoes P-methylation and, like a conventional PR3 ligand, will substitute CO ligands in transition metal complexes; the structures of the complexes [Wσ,η3-C6H4(PH2)(PCOH}CHC6H4Me-4})-1,2}(CO)(η-C5H5)], [WlC6H4(PH2)(PMe}CO}CH2C6H4Me-4})-1,2}(CO)(η-C5H5)]·(1/2C4H8O), and [WCo3(η3-CR)µ-C6H4(PH2)(PCOH}CHC6H4Me-4})-1,2}(CO)9(η-C5H5)](R = H or Me) have been determined by single crystal X-ray diffraction studies.

  将单核烷基炔配合物[WCC6H4Me-4(CO)2(δ--C5H5)]与一个当量的双齿膦C6H4(PH2)2â1,2进行处理，可得到金属-膦配合物[WÏ,δ-3-C6H4(PH2)(PCOH}CHC6H4Me-4})-1、2}(CO)(δ--C5H5)]，它在螯合环的中心磷原子上有一个未使用的孤对电子，会发生 P-甲基化反应，就像传统的 PR3 配体一样，可以替代过渡金属配合物中的 CO 配体；络合物[WÏ,δ-3-C6H4(PH2)(PCOH}CHC6H4Me-4})-1,2}(CO)(δ--C5H5)]、[WlC6H4(PH2)(PMe}CO}CH2C6H4Me-4})-1,2}(CO)(δ--C5H5)]Â-(1/2C4H8O)的结构、和[WCo3(δ-3-CR)µ-C6H4(PH2)(PCOH}CHC6H4Me-4})-1,2}(CO)9(δ--C5H5)]（R = H 或 Me）已通过单晶 X 射线衍射研究确定。

表征谱图