12154-91-5

Upstream product

• 201230-82-2 carbon monoxide 
• 536-74-3 phenylacetylene 
• 15226-74-1 dicobalt octacarbonyl 
• 15041-50-6 tetracobaltdodecacarbonyl 
• 123676-35-7 (Me)(H)(Cl)Si{(η2-CCPh)Co2(CO)6} 
• 137928-05-3 (methyl){(η2-phenylethynyl)dicobalthexacarbonyl}silane 
• 123676-33-5 methyl(phenylethynyl)silane 
• 10177-59-0 1,2-bis(dimethylarsino)tetrafluorocyclobutene 

Downstream Products

• 12078-25-0 dicarbonylcyclopentadienylcobalt 
• 123745-44-8 tetracarbonyl{μ-{(η2:η2-ethynyl)benzene}}-bis(trimethyl phosphite)-dicobalt(Co-Co) 
• 84896-09-3 pentacarbonyl{μ-{(η2:η2-ethynyl)benzene}}(trimethyl phosphite)dicobalt-(Co-Co) 
• 116896-56-1 3a,4,5,6,7,7a-hexahydro-4,7-methano-2-phenyl-1H-inden-1-one 
• 122422-20-2 1,3,3a,6a-tetrahydro-5-phenyl-4H-cyclopentafuran-4-one 
• 122474-08-2 Co₂(CO)5(HC₂Ph)(PBu₃) 
• 55926-07-3 pentacarbonyl{μ-{(η2:η2-ethynyl)benzene}}triphenylphosphinedicobalt-(Co-Co) 
• 14515-69-6 diphenylacetylene hexacarbonyl dicobalt 
• 38599-39-2 1-(trimethylsilyl)-1-propyne, dicobalt-hexacarbonyl complex 

Relevant academic research and scientific papers

Formation of a cluster-substituted cyclopentadienone from PhC2CCo3(CO)9. Crystal structure of Ph2C4C(O)2

The cluster-substituted alkyne PhCCCCo3(CO)9 (1), obtained by a coupling reaction between BrCCo3(CO)9 and PhCCH, rearranges to give the cyclopentadienone Ph2C4C(O)2 (2).Alkyne 1 with Co2(CO)8 gives PhC2CCo3(CO)9 (3).Compound 2 was characterised by X-ray crystallography at 123 K.The structure is that of a symmetrically substituted cyclopentadienone with tricobaltcarbon cluster moieties substituted α to the carbonyl group and phenyl substituents in the β positions.Various findings suggest that the formation of 2 does not proceed via a meta llacycle.Electrochemical data shows that the clusters and the cyclopentadienone ring act as independent redox centres, indicating that there is no contiguous ?-interaction.

INSERTION REACTIONS OF 2-(ARYLAZO)ARYLTRICARBONYLCOBALT

In contrast to o-metallated azobenzene-palladium complexes, 2-(phenylazo)-phenyltricarbonylcobalt is shown to undergo insertion of styrene, methyl acrylate, acrylonitrile and dimethyl fumarate as well as certain alkynes.New tricarbonylcobalt complexes derived from azotoluene, azoanisole and N-t-butylbenzaldimine and a new route to the azobenzene-derived complex are described.

Synthese und Reaktionsverhalten von (η2-BrCCR)Co2(CO)6. Die Festk?rperstruktur von Pentacarbonyl-[μ-(1,2,3,4-η:1,4-η)-1,4-diphenyl-1,3-butadien-1,4- diyl]dicobalt

The reaction of BrCCR (1a, R=nPr; 1b, R=nBu; 1c, R=SiMe3; 1d, R=Ph) with Co2(CO)8 (2) in a 1:1 molar ratio produces the hexacarbonyldicobalt complexes (η2-BrCCR)Co2(CO)6 (3a, R=nPr; 3b, R=nBu; 3c, R=SiMe3; 3d, R=Ph) in moderate yields. Apart from these complexes, pentametallic cobalt clusters of the general composition Co5(CO)12(CCR) (4a, R=nPr; 4b, R=nBu; 4c, R=SiMe3; 4d, R=Ph) are formed. Treatment of 1d with Na[Co(CO)4] (5) yields the butadi-1,3-yne complex [(η2-CCPh)Co2(CO)6]2 (6). A possible reaction mechanism for the formation of complexes 4 and 6 is described. The reaction of 4d with P(OiPr)3 (7) leads to a cluster degradation and the formation of Co2(CO)6[P(OiPr)3]2 (8). In contrast, on addition of HCCPh (9) to 4d the dicarbonyl(η4-tricarbonylcobaltacyclopentadiene) cobalt complex [η5-(PhC=CH-CH=CPh)Co(CO)3]Co(CO)2 (10) is obtained along with (η2-HCCPh)Co2(CO)6 (11). Complex 10 was characterized by single crystal X-ray crystallography. Homobimetallic 10 features a 5-membered PhC=CH-CH=CPh-Co(CO)3 ring, which is η5-coordinated to a Co(CO)2 fragment.

Synthesis, Coordination Study, and Catalytic Pauson-Khand Reactions of QuinoxP*(CO)4-μ-Alkyne Dicobalt Complexes

The coordination of the P-stereogenic and sterically demanding bisphosphine QuinoxP* to μ-alkyne dicobalt hexacarbonyl complexes was studied experimentally and computationally. Whereas the coordination occurred exclusively in a chelating fashion, the diastereoselectivity was highly substrate dependent. However, it could be explained from the computed structure and energies of the different coordination modes. The fluxional behavior of these complexes was also studied computationally. Their performance as catalysts for the Pauson-Khand reaction was explored, and outstanding reactivity was observed. Although the asymmetric induction was low to moderate, the stereochemical outcome could be mechanistically rationalized. This report provides promising results in terms of reactivity and mechanistic understanding for further developments of highly active chiral catalysts for intermolecular Pauson-Khand reactions.

Phosphorus-Sulfur Bond Cleavage at a Mixed-metal Centre; Reaction of 5-C5H5)> with PPh2(SPh)

The bimetallic cobalt-molybdenum complex 5-C5H5)> reacted with phenylacetylene in benzene to give the bimetallic alkyne-bridged complex 5-C5H5)> 1 as the major product and the trimetallic alkylidyne-capped complex 3-CCH2Ph)(CO)8(η5=C5H5)> 2 as the minor product.Reaction of 1 with PPh2(SPh) resulted in substitution of a carbonyl group on the cobalt atom to give (OC)2Co(μ-PhCCH)Mo(CO)2(η5-C5H5)> 3.Thermolysis of 3 in refluxing toluene afforded, as the major product, the complex 5-C5H5)(OC)Mo(μ-PPh2CH=CPh)(μ-SPh)Co(CO)2> 4, in which the unsymmetrical alkyne in 3 has been incorporated into a four-membered metallacycle, , such that the phenyl substituent is positioned on the carbon atom remote from the phosphide group.The related complex 5-C5H5)(OC)Mo(μ-PPh2CH=CPh)(μ-SPh)Co(CO)(PPh3)> 5, in which one of the carbonyl groups on the cobalt atom in 4 has been substituted by a triphenylphosphine ligand, has also been isolated as a minor product from this reaction.Conversion of 4 into 5 has been achieved separately by reaction of 4 with PPh3.Similarly, reaction of PPh2(SPh) with 4 yields a related compound 5-C5H5)(OC)Mo(μ-PPh2CH=CPh)(μ-SPh)Co(CO)> 6, in which the same carbonyl group on the cobalt atom has been substituted by PPh2(SPh).Single-crystal X-ray diffraction studies have been performed on complexes 2, 4 and 6.

Carbamate as an accelerating group in intermolecular Pauson-Khand reaction

The Pauson-Khand reaction (PKR) is a powerful means for the construction of cyclopentenones. However, its applications have been limited to the intramolecular version of this reaction because poor yield and regioselectivity are often the major problems in intermolecular PKR. Here we describe that a carbamate moiety in alkene substrate accelerates this intermolecular PKR. The reaction of N-4-dimethylaminophenyl O-allyl carbamate with alkyne-cobalt complex gave cyclopentenones in high yield (up to 90%) and regioselectivity (>9:1).

Unraveling factors leading to efficient norbornadiene-quadricyclane molecular solar-thermal energy storage systems

Developing norbornadiene-quadricyclane (NBD-QC) systems for molecular solar-thermal (MOST) energy storage is often a process of trial and error. By studying a series of norbornadienes (NBD-R2) doubly substituted at the C7-position with R = H, M

The Pauson-Khand reaction of medium sized trans-cycloalkenes

Medium sized trans-cycloalkenes are unusually reactive in the intermolecular Pauson-Khand reaction (PKR) with regard to typical monocyclic alkenes. This is due to the ring strain imparted by the E stereochemistry. The PKR of these alkenes offers a modular, regioselective and straightforward entry to trans fused [n.3.0] bicyclic scaffolds (n = 6-8). The Royal Society of Chemistry.

Pauson-Khand reactions in a photochemical flow microreactor

Pauson-Khand reactions were achieved at ambient temperature without any additive using a photochemical flow microreactor. The efficiency of the reaction was better than that in a conventional batch reactor, and the reaction could be operated continuously for 1 h.

The photochemistry of (μ2-RC2H)Co2(CO)6 species (R=H or C6H5), important intermediates in the Pauson-Khand reaction

The photochemistry of (μ2-RC2H)Co2(CO)6 (R=H or C6H5) has been investigated by both time-resolved and steady-state techniques. Pulsed excitation in cyclohexane solution with λexc