Mononuclear anionic formyl complexes; synthesis and properties

Selover, J. C.; Marsi, Marianne; Parker, David W.; Gladysz, J. A.

doi:10.1016/s0022-328x(00)83029-6

Cited by 25 publications

(14 citation statements)

References 32 publications

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“…These calculations suggested that nucleophiles (e.g., hydrides and alkoxides) could react with a Mn(I)-bound carbonyl ligand, thereby resulting in the formation of Mn formyl or acyl complexes (Figure a). This finding was supported by results from a literature study. − Experiments were performed to substantiate the computational results.…”

Section: Resultssupporting

confidence: 89%

“…This finding was supported by results from a literature study. 32 − 37 Experiments were performed to substantiate the computational results.…”

Section: Resultsmentioning

confidence: 99%

“…This is similar to what was observed by Gladysz and co-workers, although no organic products were observed with GC-MS after decomposition to the manganate salt (i.e., we did not observe the expected isopropyl propionate ester). 37 The combination of potassium isopropoxide with 1 resulted in formation of dialkoxycarbonyl 2 and Mn-isopropoxo-dimer 3 . Thus, complex 2 appears to originate from the sequential addition of KO i Pr to Mn(CO) 5 Br, and then to 1 .…”

Section: Resultsmentioning

confidence: 99%

“…This decomposition process is accelerated by the addition of trialkylboranes, although the underlying mechanism is not completely understood. 37 …”

Section: Resultsmentioning

confidence: 99%

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Manganese-Mediated C–C Bond Formation: Alkoxycarbonylation of Organoboranes

et al. 2021

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Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C–C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C–C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester’s substitution (e.g., OMe, O t Bu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.

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“…These calculations suggested that nucleophiles (e.g., hydrides and alkoxides) could react with a Mn(I)-bound carbonyl ligand, thereby resulting in the formation of Mn formyl or acyl complexes (Figure a). This finding was supported by results from a literature study. − Experiments were performed to substantiate the computational results.…”

Section: Resultssupporting

confidence: 89%

“…This finding was supported by results from a literature study. 32 − 37 Experiments were performed to substantiate the computational results.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…This decomposition process is accelerated by the addition of trialkylboranes, although the underlying mechanism is not completely understood. 37 …”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Manganese-Mediated C–C Bond Formation: Alkoxycarbonylation of Organoboranes

et al. 2021

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“…These calculations suggested that nucleophiles (e.g., hydrides and alkoxides) could react with a Mn(I)-bound carbonyl ligand, thereby resulting in the formation of Mn formyl or acyl complexes. These findings are in line with prior experimental observations [38][39][40][41][42][43][44][45] and strongly imply that such reaction paths need to be accounted for when constructing mechanistic hypotheses to rationalize catalytic results based on the in situ catalyst generation protocol employing the activation of Mn(I) carbonyl precursors in the presence of a strong nucleophile alkoxide base.…”

Section: 1case Study I: Mn(co)5br Pre-catalyst Activationsupporting

confidence: 86%

ReNeGate: Reaction Network Graph Theoretical tool for automated mechanistic studies in computational homogeneous catalysis

Hashemi

Bougueroua

Gaigeot

et al. 2022

Preprint

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Exploration of the chemical reaction space of chemical transformations in multicomponent mixtures is a challenge for modern computational protocols. In order to remove expert bias from mechanistic studies and to discover new chemistries, an automated graph-theoretical methodology is proposed to provide mechanistic analysis in catalytic systems. The primary advantage of the presented three-step approach over the existing automated pathways generation methods is the integrated ability to handle multicomponent catalytic systems of arbitrary complexity (mixtures of reactants, catalyst precursors, ligands, additives, and solvent). It is not limited to pre-defined chemical rules, does not require pre-alignment of reaction mixture components consistent with a reaction coordinate and is not agnostic to the chemical nature of transformations. Conformer exploration, Reactive event identification and Reaction network analysis are the main steps taken for understanding the underlying mechanistic pathways in catalytic mixtures given the reaction mixture as the input. Such a methodology allows to comprehensively explore the catalytic systems in realistic conditions for either previously observed or completely unknown reactive events. The expert bias is sought to be removed in either of the steps and chemical intuition is limited to the choice of the thermodynamic constraint imposed by the applicable experimental conditions in terms of threshold energy values for allowed transformations. The capabilities of the proposed methodology have been tested by exploring reactivity of Mn complexes relevant for catalytic hydrogenation chemistry to verify previously postulated activation mechanisms and unravel unexpected reaction channels relevant to rare deactivation events.

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Potassium Triethylborohydride

Zaidlewicz¹,

Brown²

2001

Encyclopedia of Reagents for Organic Synthesis

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Mononuclear anionic formyl complexes; synthesis and properties

Cited by 25 publications

References 32 publications

Manganese-Mediated C–C Bond Formation: Alkoxycarbonylation of Organoboranes

Manganese-Mediated C–C Bond Formation: Alkoxycarbonylation of Organoboranes

ReNeGate: Reaction Network Graph Theoretical tool for automated mechanistic studies in computational homogeneous catalysis

Potassium Triethylborohydride

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