dicobalt octacarbonyl

• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 各种混合金属/非金属
• 英文名称: dicobalt octacarbonyl
• 英文别名: Co₂(CO)₈；octacarbonyldicobalt；cobalt carbonyl；carbon monoxide;cobalt
• 化学式: 8CO*2Co
• 分子量: 342.07
• InChiKey: UMYVESYOFCWRIW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  dicobalt octacarbonyl 在 sodium amaggam 作用下， 以 四氢呋喃 为溶剂， 生成 sodium tetracarbonyl cobaltate
  参考文献：
  名称：

  Bonding Behavior of Co(CO)₃L (L = CO, PPh₃) Building Blocks in Platinum−Cobalt Carbonyl Clusters

  摘要：

  The reaction of [Co(CO)(4)](-) with [Pt2Cl(mu-PPh2)(PPh3)(3)] (1:1 ratio), which was prepared in situ by reaction of aqueous HCl with the orthometalated complex [Pt-2(mu-PPh2)(mu-o-C6H4PPh2)(PPh3)(2)], afforded the deep green triangular cluster [Pt2Co(mu-PPh2)(CO)(4)(PPh3)(2)], 7. X-ray crystallographic analysis reveals that this new cluster contains two formally monoanionic fragments, PPh2- and CO(CO)(4)(-), that bridge a d(9)-d(9) Pt(l)-Pt(l) metal-metal bond. Whereas tetracarbonylcolbaltate is generally bonded to only one metal center as a 2e donor ligand, it is best viewed here as a formally 4e donor anionic metalloligand. This model leads then to the usual 16e count for each Pt center and relates this metalloligand to other anionic bridging ligands, such as PPh2-. A comparative EHMO bonding analysis of [CO(Co)(3)L](--) (L = CO, PR3) fragments is presented which takes into account the possible coordination geometries about cobalt, trigonal bipyramidal (with C-3nu local symmetry) or edge-capped tetrahedral when referring to the ligand polyhedron (with C-2nu or C-s symmetry). The results support the description of this unusual bridging bonding mode.

  DOI：

  10.1021/ic010739p
• 作为产物：
  描述：

  dicobalt octacarbonyl 以 甲苯 为溶剂， 生成 dicobalt octacarbonyl
  参考文献：
  名称：

  In situ high pressure FT-IR spectroscopy on alkene hydroformylation catalysed by RhH(CO)(PPh3)3 and Co2(CO)8

  摘要：

  Catalytic hydroformylation of olefins has been carried out in a HP FT-IR cell using RhH(CO)(PPh3)(3) catalytic precursor. A different behaviour was noticed between a terminal (hex-1-ene) and an internal alkene (cyclohexene) and different rate-determining steps of the catalytic cycle have been hypothesised. The hydroformylation of hex-1-ene has also been tested in the presence of Co-2(CO)(S) as catalyst. In this case, only the catalytic precursor is evidenced by HP FT-IR. Finally, the influence of an additional gas (helium. nitrogen or argon) in the reaction medium was evaluated: a high pressure of argon or nitrogen affects the initial rate of the reaction as shown by a decrease of the rate of the aldehyde formation. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2004.07.021
• 作为试剂：
  描述：

  13-bromo-17,18-dihydro-10-mesityl-18,18-dimethylporphyrin 、 ethyl potassium malonate 在 咪唑 、 dicobalt octacarbonyl 、 palladium diacetate 、 三乙胺 、 4,5-双二苯基膦-9,9-二甲基氧杂蒽 、 magnesium chloride 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以62%的产率得到13-(3-ethoxy-3-oxopropanoyl)-10-mesityl-18,18-dimethylchlorin
  参考文献：
  名称：

  叶绿素激发的红色区域荧光团：在水性介质中的构建基合成和研究。

  摘要：

  在红色光谱区域（600-700 nm）吸收和发射的荧光团在光化学和光医学中引起了极大的兴趣。已经设计并合成了八种不同极性的新目标二氢卟酚（共19种新二氢卟酚）-叶绿素类似物；7个二氢卟酚配有可生物偶联的系链。非极性有机溶剂（甲苯），极性有机溶剂（DMF）以及水性或水性胶束介质中的疏水性或两亲性二氢卟酚在红色区域显示出清晰的发射带，并且荧光量子产率适中（Φf= 0.2-0.3）。泊松分析表明，大多数胶束是空的，很少包含＞ 1的二氢卟酚。各自带有三个PEG（低聚乙二醇）基团的水溶性二氢卟酚显示出窄的发射带（半峰全宽最大<25 nm）。最低单线态激发态的寿命以及人口减少途径（荧光，系统间杂交，内部转化）的相应产率和速率常数通常不受PEG基团或在水性或有机介质中溶解的影响。一组二氢卟酚-抗生物素蛋白缀合物显示Φf增加2倍，平均二氢卟酚/抗生物素蛋白比率增加（2.3-12）。总之，本文所述的各种极性

  DOI：

  10.3390/molecules23010130

文献信息

• Silylations of α,β-unsaturated and aromatic carbonyl compounds with cobalt carbonyls
  作者：Attila Sisak

  DOI：10.1016/s0022-328x(99)00228-4

  日期：1999.7

  [η3-η5-(Silyloxy–alkenyl)]-cobalt carbonyls and various silyl ethers were formed in the cobalt carbonyl mediated silylations of α,β-unsaturated and aromatic carbonyl compounds. A silyloxonium tetracarbonylcobaltate tight ion pair was suggested as a common intermediate, which provides the products through a radical pair in the cases of aromatic aldehydes and ketones.

  [η 3 -η 5 - （甲硅烷基氧基-链烯基）] -形成于α，β不饱和和芳族羰基化合物的羰基钴介导silylations羰基钴和各种甲硅烷基醚。有人建议使用四羰基钴酸甲硅氧鎓的紧密离子对作为常见的中间体，在芳香族醛和酮的情况下，可通过自由基对提供产物。
• Tandem Use of Cobalt-Mediated Reactions to Synthesize (+)-Epoxydictymene, a Diterpene Containing a <i>Trans</i>-Fused 5−5 Ring System
  作者：Timothy F. Jamison、Soroosh Shambayati、William E. Crowe、Stuart L. Schreiber

  DOI：10.1021/ja970022u

  日期：1997.5.1

  (+)-epoxydictymene has been synthesized in 20 steps using the asymmetry of (R)-pulegone and several substrate-controlled diastereoselective reactions to prepare the natural product in its natural configuration. Three of the four rings were assembled with two consecutive intramolecular reactions involving dicobalt hexacarbonyl complexes of alkynes: a Lewis acid-promoted Nicholas reaction and a Pauson−Khand reaction

  二萜 (+)-epoxydictymene 已使用 (R)-pulegone 的不对称性和几种底物控制的非对映选择性反应在 20 个步骤中合成，以制备其天然构型的天然产物。四个环中的三个通过涉及炔烃的六羰基二钴配合物的两个连续分子内反应组装：路易斯酸促进的尼古拉斯反应和 Pauson-Khand 反应。天然产物的应变反式-3-氧杂双环[3.3.0]辛烷环系统的构建提出了重大挑战。为此，研究了几种自由基和阴离子环化，后者导致 (+)-epoxydictymene。
• Dicobalt hexacarbonyl-3-butyn-1-yl cobaloxime: synthesis X-ray crystal structure and reactions of the first combined cobaloxime–dicobalt hexacarbonyl alkyne complex
  作者：Michael P Coogan、Lisa S Stanton、Thilo Walther

  DOI：10.1016/s0022-328x(03)00385-1

  日期：2003.7

  Reaction of 1-butynyl cobaloxime (1), synthesised by displacement of the corresponding tosylate with cobaloximato nucleophile, with dicobalt octacarbonyl gives the first trimetallic cobaloxime–dicobalt hexacarbonyl-alkyne complex (2). This trimetallic species is characterised by X-ray crystallography and undergoes the Pauson-Khand reaction to give cobaloxime-substituted cyclopentenones. We believe

  通过将相应的甲苯磺酸酯与钴氧肟基亲核试剂置换而合成的1-丁炔基钴氧肟（1）与二钴二辛酸八羰基酯反应生成了第一个三金属钴肟-二钴六羰基炔烃络合物（2）。该三金属物质通过X射线晶体学表征，并进行Pauson-Khand反应，得到钴肟肟取代的环戊烯酮。我们认为，这是炔烃的Pauson-Khand反应的第一个例子，其中炔烃具有碳-金属sigma键。
• Reaction of octacarbonyldicobalt with the free radicals galvinoxyl and 2,2-diphenyl-1-picrylhydrazyl. Attempts to scavenge the tetracarbonylcobalt radical
  作者：Róbert Tuba、Ferenc Ungváry

  DOI：10.1016/s0020-1693(02)00853-8

  日期：2002.5

  The addition of galvinoxyl or 2,2-diphenyl-1-picrylhydrazyl to octacarbonyldicobalt in n-octane solution results in the loss of all carbon monoxide ligands and the formation of Co(II)-containing products.

  在正辛烷溶液中向八羰基二钴中加入加尔万氧基或2,2-二苯基-1-吡啶并肼基会损失所有一氧化碳配体，并形成含Co（II）的产物。
• Organometallic derivatives of natural products: dicobalt hexacarbonyl complexes of geranyl-alkynes
  作者：Angela Moore、Johannes Ostermann、Yannick Ortin、Michael J. McGlinchey

  DOI：10.1039/c6nj00622a

  日期：——

  migration to form previously unknown E and Z 1-methoxy-3,7-dimethyl-1,6-octadiene in low yield. Sodium propargyl alkoxide and geranyl bromide yield propargyl geranyl ether, 13; subsequent reaction with dicobalt octacarbonyl and then bis(diphenylphosphino)methane furnishes the corresponding alkyne–Co2(CO)4(dppm) tetrahedral cluster, 16. Reaction of geranylacetone with phenylethynyl-lithium, and then with

  用二铁九碳羰基处理甲基香叶基醚会导致氢迁移，从而以低收率形成以前未知的E和Z 1-甲氧基-3,7-二甲基-1,6-辛二烯。炔丙基醇钠和香叶基溴化物产生炔丙基香叶基醚，13。随后与二羰基二钴八羰基反应，然后与双（二苯基膦基）甲烷反应，得到相应的炔烃-Co 2（CO）4（dppm）四面体簇，16。香叶基丙酮与苯基乙炔基锂反应，然后与Co 2（CO）8反应形成（1-苯基-3,7,11-三甲基十二烷基-6,10-二烯-1-yn-3-醇）Co 2（CO ）6，19。可以通过适当的醇与三氯乙酰氯和然后的Co 2（CO）8反应，以非常好的收率制得carbynyltricobaltnona羰基簇RC（O）CCo 3（CO）9，其中R =香叶基23或法呢基25。，或与金属稳定的离子[Co 3（CO）9 C C O] +，24反应。潜在用途的这些（η 2 -alkyne）在Pauson-Khand反应或尼古拉斯环化二钴复合物进行了讨论。