Übergangsmetall—carbin-komplexe

Fischer, Ernst Otto; Schambeck, W.

doi:10.1016/s0022-328x(00)92586-5

Cited by 37 publications

(3 citation statements)

References 14 publications

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“…Organorhenium oxides have been examined for oxidation catalysis as early as 1963 127. A series of new organorhenium oxides such as η 5 ‐(C 5 (CH 3 ) 5 )ReO 3 and (CH 3 )ReO 3 have been synthesized in the last few decades 128.…”

Section: Catalysts For Lignin Oxidative Conversionmentioning

confidence: 99%

Catalytic Oxidation of Biorefinery Lignin to Value‐added Chemicals to Support Sustainable Biofuel Production

2014

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Transforming plant biomass to biofuel is one of the few solutions that can truly sustain mankind's long-term needs for liquid transportation fuel with minimized environmental impact. However, despite decades of effort, commercial development of biomass-to-biofuel conversion processes is still not an economically viable proposition. Identifying value-added co-products along with the production of biofuel provides a key solution to overcoming this economic barrier. Lignin is the second most abundant component next to cellulose in almost all plant biomass; the emerging biomass refinery industry will inevitably generate an enormous amount of lignin. Development of selective biorefinery lignin-to-bioproducts conversion processes will play a pivotal role in significantly improving the economic feasibility and sustainability of biofuel production from renewable biomass. The urgency and importance of this endeavor has been increasingly recognized in the last few years. This paper reviews state-of-the-art oxidative lignin depolymerization chemistries employed in the papermaking process and oxidative catalysts that can be applied to biorefinery lignin to produce platform chemicals including phenolic compounds, dicarboxylic acids, and quinones in high selectivity and yield. The potential synergies of integrating new catalysts with commercial delignification chemistries are discussed. We hope the information will build on the existing body of knowledge to provide new insights towards developing practical and commercially viable lignin conversion technologies, enabling sustainable biofuel production from lignocellulosic biomass to be competitive with fossil fuel.

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Section: Catalysts For Lignin Oxidative Conversionmentioning

confidence: 99%

Catalytic Oxidation of Biorefinery Lignin to Value‐added Chemicals to Support Sustainable Biofuel Production

2014

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“…Fluorid läßt sich auch an den Phenylcarbin-Komplex [(C 5 H 5 )(CO)2MnCC 6 H5]SbCl6 [7] addieren. Reaktionen von [(C 5 H5)(CO)2MnCC 6 H5]BCl4 mit anderen Nucleophilen (Alkoholate, Phenolate [8], Cyanat [9], Cyanid, Isothiocyanat [10]) hatten uns bereits früher zu den entsprechenden Carben-Komplexen geführt.…”

Section: 3unclassified

Übergangsmetall-Garben-Komplexe, CXXI [1] Fluorcarbenkomplexe des Mangans / Transition Metal Carbene Complexes, CXXI [1] Fluorocarbene Complexes of Manganese

Univ¹,

Kleine

Schambeck

et al. 1981

Zeitschrift Für Naturforschung B

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Abstract The reaction between CH3Cs5H4Mn(CO)3 and LiN(C2H5)2 and subsequent alkylation with [(C2H5)3O]BF4 affords CH3C5H4(CO)2MnC(OC2H5)N(C2H5)2. This carbene complex reacts with borontrihalides BX3 (X = F, Cl) to yield [CH3C5H4(CO)2MnCN(C2H5)2]BX4. Ad-dition of [(C4H9)4N]F to this cationic carbyne complex results in the formation of CH3C5H4(CO)2MnC(F)N(C2H5)2 . In the same way C5H5(CO)2MnC(F)C6H5 is prepared from [C5H5(CO)2MnCC6H5]SbCl6. Fluoride addition can be reversed by reaction of the latter carbene complex with BF3 to give [C5H5(CO)2MnCC6H5]BF4. In the X-ray structure of C5H5(CO)2MnC(F)C6H5 unusual bonding parameters are found, which are consistent with the easy cleavage of the C(carbene)-F bond.

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“…Indeed, both cases have been observed in the analogous carbyne reactions. 27,33,35,36 Preliminary DFT studies have provided evidence for an initial nucleophilic attack of the base at the boron center. 2 Herein we report experimental evidence for the proposed mechanistic route.…”

Section: Introductionmentioning

confidence: 99%

Isolation of the key intermediates of base-promoted borylene–carbonyl coupling reactions

et al. 2014

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The terminal alkylborylene complex [(h 5 -C 5 H 5 )(OC) 2 Mn]BtBu] (1) reacts with trimethylphosphine and CO to form a borylene-carbonyl coupling productThis reactivity can be extended to nitrogen-and carbon-based ligands to form similar complexes and IMe, 8). The key intermediates of these reactions were found to be neutral, Lewis base-stabilized borylenes of the form [(h 5 -C 5 H 5 )(OC) 2 Mn]B(tBu)(L)] (L ¼ 4-dimethylaminopyridine (DMAP), 4, 3,5-lutidine, 5 and :C[N(Me)CH] 2 (IMe), 6, which have been isolated and fully characterized. They can be synthesized from simple addition of the base to the parent borylene 1. The coordination of the base to the boron center seems to facilitate a rearrangement of the t-butyl borylene substituent.

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Übergangsmetall—carbin-komplexe

Cited by 37 publications

References 14 publications

Catalytic Oxidation of Biorefinery Lignin to Value‐added Chemicals to Support Sustainable Biofuel Production

Catalytic Oxidation of Biorefinery Lignin to Value‐added Chemicals to Support Sustainable Biofuel Production

Übergangsmetall-Garben-Komplexe, CXXI [1] Fluorcarbenkomplexe des Mangans / Transition Metal Carbene Complexes, CXXI [1] Fluorocarbene Complexes of Manganese

Isolation of the key intermediates of base-promoted borylene–carbonyl coupling reactions

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