Organic Synthesis using Transition Metal Carbonyl Complexes

Söderberg, Björn C.G.

doi:10.1002/9781119951438.eibc0155

Cited by 5 publications

(4 citation statements)

References 115 publications

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“…When oleylamine is added to the chloro oleyl niobium(V), we observe the emergence of a N−H peak at 7.64 ppm indicative of amide formation caused by the aminolysis of niobium oleate (Figure 2b). 47 The proton from the amine that is removed during aminolysis forms OH − and the metal oxo species is formed as all the amine is used in the reaction. The acidic proton from the remaining oleic acid reappears after the metal oxo species is formed as there is no further interaction with free Cl − or oleylamine.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Electrochromic Niobium Oxide Nanorods

et al. 2019

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Niobium oxide (Nb 2 O 5 ) is an interesting active material for technologies ranging from catalysis and sensors to energy storage and electrochromic devices owing to its unique optical, electronic, and electrochemical properties. These properties vary between different phases and morphologies in the Nb 2 O 5 system, but systematic studies that correlate properties to phase and morphology are limited by current synthetic methods, which require postsynthetic high temperature treatments and suffer from a lack of direct and precise control over morphology, crystal structure, and stoichiometry. Here, we report a heat-up colloidal synthesis method that produces orthorhombic Nb 2 O 5 nanorods 1 nm in width by 31 nm in length that preferentially grow along the [001] direction. The synthesis is based on aminolysis of niobium oleate in octadecene, and nanorods are formed through three distinct steps: aminolysis-driven formation of niobium oxo clusters, condensation into amorphous Nb 2 O 5 seeds below the reaction temperature (240 °C, under atmospheric pressure), and crystallization and growth of Nb 2 O 5 nanorods. We investigated the electrochromic behavior of nanorod thin films upon Li + intercalation and observed predominantly near-infrared coloration, fast switching kinetics, and durability for at least 500 charge−discharge cycles.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Electrochromic Niobium Oxide Nanorods

et al. 2019

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“…It is suggested here that decarboxylation can occur via either the formation of an aminium radical cation (e.g., formed after an initial electron abstraction from the neutral amine) or the iminium cation (imine p K a values are usually near neutral pH) (Scheme ). − In both cases, a decarboxylated imine is released, which is mostly oxidized to nitrile …”

Section: Results and Discussionmentioning

confidence: 99%

Reaction of Amino Acids with Ferrate(VI): Impact of the Carboxylic Group on the Primary Amine Oxidation Kinetics and Mechanism

Rougé

Nguyen

Allard

et al. 2022

Environ. Sci. Technol.

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Ferrate (Fe(VI)) is a novel oxidant that can be used to mitigate disinfection byproduct (DBP) precursors. However, the reaction of Fe(VI) with organic nitrogen, which is a potential precursor of potent nitrogenous DBPs, remains largely unexplored. The present work aimed to identify the kinetics and products for the reaction of Fe(VI) with primary amines, notably amino acids. A new kinetic model involving ionizable intermediates was proposed and can describe the unusual pH effect on the Fe(VI) reactivity toward primary amines and amino acids. The Fe(VI) oxidation of phenylalanine produced a mixture of nitrile, nitrite/nitrate, amide, and ammonia, while nitroalkane was an additional product in the case of glycine. The product distribution for amino acids significantly differed from that of uncarboxylated primary amines that mainly generate nitriles. A general reaction pathway for primary amines and amino acids was proposed and notably involved the formation of imines, the degradation of which was affected by the presence of a carboxylic group. In comparison, ozonation led to higher yields of nitroalkanes that could be readily converted to potent halonitroalkanes during chlor(am)ination. Based on this study, Fe(VI) can effectively mitigate primary amine-based, nitrogenous DBP precursors with little formation of toxic halonitroalkanes.

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“…Metal carbonyl complexes (MCCs) and their derivatives are an important class of substances in modern chemistry. Their relevance includes being reagents and catalysts in synthesis [1,2], and potential pharmaceuticals [3][4][5][6]. In macrochemistry, MCCs are usually synthesized under high pressures of CO-gas and elevated temperatures from either a metal powder or metal compound.…”

Section: Introductionmentioning

confidence: 99%

The influence of chemical parameters on the in-situ metal carbonyl complex formation studied with the fast on-line reaction apparatus (FORA)

et al. 2021

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A new setup named Fast On-line Reaction Apparatus (FORA) is presented which allows for the efficient investigation and optimization of metal carbonyl complex (MCC) formation reactions under various reaction conditions. The setup contains a 252Cf-source producing short-lived Mo, Tc, Ru and Rh isotopes at a rate of a few atoms per second by its 3% spontaneous fission decay branch. Those atoms are transformed within FORA in-situ into volatile metal carbonyl complexes (MCCs) by using CO-containing carrier gases. Here, the design, operation and performance of FORA is discussed, revealing it as a suitable setup for performing single-atom chemistry studies. The influence of various gas-additives, such as CO2, CH4, H2, Ar, O2, H2O and ambient air, on the formation and transport of MCCs was investigated. O2, H2O and air were found to harm the formation and transport of MCCs in FORA, with H2O being the most severe. An exception is Tc, for which about 130 ppmv of H2O caused an increased production and transport of volatile compounds. The other gas-additives were not influencing the formation and transport efficiency of MCCs. Using an older setup called Miss Piggy based on a similar working principle as FORA, it was additionally investigated if gas-additives are mostly affecting the formation or only the transport stability of MCCs. It was found that mostly formation is impacted, as MCCs appear to be much less sensitive to reacting with gas-additives in comparison to the bare Mo, Tc, Ru and Rh atoms.

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Organic Synthesis using Transition Metal Carbonyl Complexes

Abstract: Synthetic transformations using transition metal carbonyl carbene, arene, diene, and alkyne complexes are discussed. Reaction of synthetic importance and applications in organic total synthesis are included.

Cited by 5 publications

References 115 publications

Electrochromic Niobium Oxide Nanorods

Electrochromic Niobium Oxide Nanorods

Reaction of Amino Acids with Ferrate(VI): Impact of the Carboxylic Group on the Primary Amine Oxidation Kinetics and Mechanism

The influence of chemical parameters on the in-situ metal carbonyl complex formation studied with the fast on-line reaction apparatus (FORA)

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