Cyclotrimerization of acetylenes catalyzed by (η5-cyclopentadienyl)rhodium complexes

Abdulla, Khalid; Booth, Brian L.; Stacey, Catherine

doi:10.1016/0022-328x(85)80250-3

Cited by 65 publications

(43 citation statements)

References 31 publications

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“…In fact, on the basis of the experimental evidence reported by Booth et al, [10] if the IndRh fragment is used instead of the CpRh fragment the initial rate is up to ten times faster. In fact, on the basis of the experimental evidence reported by Booth et al, [10] if the IndRh fragment is used instead of the CpRh fragment the initial rate is up to ten times faster.…”

Section: Acetylene [2+2+2] Cyclotrimerization: An Alternative Mechanismmentioning

confidence: 98%

Indenyl Effect Due to Metal Slippage? Computational Exploration of Rhodium‐Catalyzed Acetylene [2+2+2] Cyclotrimerization

2013

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The mechanism of CpRh (Cp=cyclopentadienyl) and IndRh (Ind=indenyl)-catalyzed acetylene [2+2+2] cyclotrimerization has been revisited aiming at finding an explanation for the better performance of the latter catalyst found experimentally. The hypothesis that an ancillary ligand of the precatalyst remains bonded to the metal center throughout the whole catalytic cycle, based on the experimental evidence that the nature of this ligand can exert some control in cocyclotrimerization of different alkynes, is considered. Strong hapticity variations occur in both the CpRh- and IndRh-catalyzed processes. As the Ind ligand undergoes a more facile slippage than Cp, the energy profile is far smoother in the IndRh-catalyzed cyclotrimerization. This difference in the energetics of the process translates into an enhanced activity of the IndRh catalyst, in nice agreement with experiment.

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Section: Acetylene [2+2+2] Cyclotrimerization: An Alternative Mechanismmentioning

confidence: 98%

Indenyl Effect Due to Metal Slippage? Computational Exploration of Rhodium‐Catalyzed Acetylene [2+2+2] Cyclotrimerization

2013

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“…The cobalt and rhodium complexes discussed above provide the first and, to date, the only examples of the use of Ramirez ylide-derived metal complexes as catalysts [18,62]. With the importance of metallocene catalysts in a variety of applications, it is surprising that so few reports of catalysis using Ramirezderived complexes exist.…”

Section: Group 9 Metalsmentioning

confidence: 95%

“…As part of a study on the cyclotrimerization of acetylenes catalyzed by various 5 -CpRh compounds, the compound [Rh(C 5 H 4 PPh 3 )(CO) 2 ][PF 6 ] was examined for its ability to trimerize dimethylacetylenedicarboxylate (DMAD) and 3-hexyne [62]. The rates of cyclotrimerization of DMAD varied in the order [Rh(C 5 H 4 PPh 3 )(CO) 2 ][PF 6 ] < 5 -CpRh(CO) 2 < 5 -Cp*Rh(CO) 2 , but all rates were in the same order of magnitude.…”

Section: Group 9 Metalsmentioning

confidence: 99%

Coordination complexes of aryl- and alkylphosphonium cyclopentadienylides (cyclopentadienylidene ylides), C5R4PR′R′′R′′′ (R=H, alkyl, aryl; R′, R′′, R′′′=alkyl, aryl)

Brownie

Baird

2008

Coordination Chemistry Reviews

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“…[74] For example, cyclotrimerization of ethyl propiolate with either 102 or 103 results in a 1:1 mixture of triesters 104 and 105 (Scheme 35a). Indenyl complex 102 can catalyze the cyclotrimerization of ethyl propiolate and propargyl alcohol 106 in an 83% yield of lactone 107 , which was observed to be the sole product (Scheme 35b).…”

Section: Cobalt Rhodium and Iridiummentioning

confidence: 99%

Indenylmetal Catalysis in Organic Synthesis

Trost

Ryan

2017

Angew Chem Int Ed

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Synthetic organic chemists have a long-standing appreciation for transition metal cyclopentadienyl complexes, of which many have been used as catalysts for organic transformations. Much less well known are the contributions of the benzo-fuzed relative of the cyclopentadienyl ligand, the indenyl ligand, whose unique properties have in many cases imparted differential reactivity in catalytic processes toward the synthesis of small molecules. In this review, we will present examples of indenylmetal complexes in catalysis and compare their reactivity to their cyclopentadienyl analogues, wherever possible.

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Cyclotrimerization of acetylenes catalyzed by (η5-cyclopentadienyl)rhodium complexes

Cited by 65 publications

References 31 publications

Indenyl Effect Due to Metal Slippage? Computational Exploration of Rhodium‐Catalyzed Acetylene [2+2+2] Cyclotrimerization

Indenyl Effect Due to Metal Slippage? Computational Exploration of Rhodium‐Catalyzed Acetylene [2+2+2] Cyclotrimerization

Coordination complexes of aryl- and alkylphosphonium cyclopentadienylides (cyclopentadienylidene ylides), C5R4PR′R′′R′′′ (R=H, alkyl, aryl; R′, R′′, R′′′=alkyl, aryl)

Indenylmetal Catalysis in Organic Synthesis

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