Fischer-Tropsch intermediates: tris[(.eta.2-formaldehyde)zirconocene] from the carbonylation of a zirconium hydride

Kropp, Kurt; Skibbe, Volker; Erker, Gerhard; Krueger, C.

doi:10.1021/ja00348a075

Cited by 77 publications

(9 citation statements)

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“…Unfortunately we were unable to isolate and to fully characterize the compound because of its ready decomposition to give TpRu(CH 3 )(CO)(PPh 3 ). The acetaldehyde complex TpRuH(PPh 3 )(CH 3 CHO) is not unusual as there are numerous examples of η 1 - and η 2 -aldehyde complexes. , …”

Section: Resultsmentioning

confidence: 99%

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

et al. 1997

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Treatment of TpRuCl(PPh 3 )(CH 3 CN) (Tp ) hydrotris(pyrazolyl)borate) with NaBH 4 in ethanol did not yield the expected hydride complex TpRuH(PPh 3 )(CH 3 CN) (2) but rather the methyl carbonyl complex TpRu(CH 3 )(CO)(PPh 3 ) (1b). Formation of 1b was due to decarbonylation of ethanol by 2 generated in situ by NaBH 4 reduction of TpRuCl(PPh 3 )(CH 3 -CN). Analogous reactions in the presence of other primary alcohols RCH 2 OH (R ) H, C 2 H 5 , n-C 3 H 7 , C 6 H 5 , C 6 H 4 CH 3 -4, and C 6 H 4 Cl-4) led to the corresponding σ-organyl complexes TpRuR(CO)(PPh 3 ). A common feature of the reactions is that the R groups of alcohols RCH 2 -OH become the σ-organyl groups in the final metal complexes. A mechanism involving metal-η 2 -aldehyde and -η 2 -dihydrogen intermediates is proposed for the decarbonylation reaction. This is supported by the observation of the η 2 -dihydrogen complex TpRuH(H 2 )-(PPh 3 ) (3) during the decarbonylation reaction. 3 was synthesized independently by heating a THF solution of 2 under 40 atm of H 2 at 60 °C for 48 h or by heating 2 in CH 3 OH at 60 °C under 6 atm of H 2 for 5-6 h.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

et al. 1997

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“…Noteworthy, no other products were observed. Formaldehyde (25) was controversially discussed as intermediate for chain growth in Fischer-Tropsch chemistry [66]. Also for CO 2 RR no evidence for C-C bond formation from formaldehyde (25) was found.…”

Section: Reactivity Of C=o Double Bondsmentioning

confidence: 99%

Reactivity of Copper Electrodes towards Functional Groups and Small Molecules in the Context of CO2 Electro-Reductions

et al. 2017

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Abstract:The direct electro-reduction of CO 2 to functional molecules like ethene is a highly desirable variant of CO 2 utilization. The formation of, for example, ethene from CO 2 is a multistep electrochemical process going through various intermediates. As these intermediates are organic species, the CO 2 reducing electro-catalyst has to be competent for a variety of organic functional group transformations to yield the final product. In this work, the activity of an in situ-grown nano-structured copper catalyst towards a variety of organic functional group conversions was studied. The model reagents were selected from the product spectrum of actual CO 2 reduction reaction (CO 2 RR) experiments and from proposals in the literature. The CO 2 bulk electrolysis benchmark was conducted at 170 mAcm −2 current density with up to 43% Faradaic Efficiency (FE) for ethene and 23% FE for ethanol simultaneously. To assure relevance for application-oriented conditions, the reactivity screening was conducted at elevated current densities and, thus, overpotentials. The found reactivity pattern was then also transferred to the CO reduction reaction (CORR) under benchmark conditions yielding additional insights. The results suggest that at high current density/high overpotential conditions, also other ethene formation pathways apart from acetaldehyde reduction such as CH 2 dimerization are present. A new suggestion for a high current density mechanism will be presented, which is in agreement with the experimental observations and the found activity pattern of copper cathodes toward organic functional group conversion.

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“…dinuclear zirconocene complexes containing (? ?2-ketene)metallocene structural subunits (8,9, and 14 in Table III and Scheme II). The C-0 bond lengths are close to the expected C(sp3)-0 bond length found for the ( 2aldehyde)ZrCp2 complexes 11, 12, and 13. Although the Zr-0 bonds within each (r;2-benzophenone)ZrCp2 moiety of 3 are slightly shorter than the comparable Zr-0 bonds in the examples cited in Table III, they are clearly longer than the Zr-0 bonds in simple (tt-oxo)zirconocene complexes such as (Cp2ZrCl)20 (1.95 Á)21 or (Cp2ZrO)3 (1.94 A).22 The Zr-C (carbonyl) bonds in 3 of 2.346 (3) and 2.350…”

Section: Scheme IIImentioning

confidence: 99%

Dimeric (.eta.2-benzophenone)zirconocene: its remarkable structure and chemistry

Erker¹,

Dorf²,

Czisch³

et al. 1986

Organometallics

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Fischer-Tropsch intermediates: tris[(.eta.2-formaldehyde)zirconocene] from the carbonylation of a zirconium hydride

Cited by 77 publications

References 4 publications

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Reactivity of Copper Electrodes towards Functional Groups and Small Molecules in the Context of CO2 Electro-Reductions

Dimeric (.eta.2-benzophenone)zirconocene: its remarkable structure and chemistry

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Fischer-Tropsch intermediates: tris[(.eta.2-formaldehyde)zirconocene] from the carbonylation of a zirconium hydride

Cited by 77 publications

References 4 publications

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H2)(PPh3) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H2)(PPh3) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Reactivity of Copper Electrodes towards Functional Groups and Small Molecules in the Context of CO2 Electro-Reductions

Dimeric (.eta.2-benzophenone)zirconocene: its remarkable structure and chemistry

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Product

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Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction

Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H₂)(PPh₃) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction