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Double Deprotonation of CH₃CN by an Iron-Aluminium Complex.

ABSTRACT: Herein we present the first double deprotonation of acetonitrile (CH₃CN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN]^2- dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CH₂CN]^- complex, which has been characterised in situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts.^[1, 2] The isolation of a [CHCN]^2- dianion through simple deprotonation of CH₃CN also offers the possibility of establishing a broader chemistry of this motif.

SUBMITTER: Stadler B

PROVIDER: S-EPMC10952947 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature

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Double Deprotonation of CH3CN by an Iron-Aluminium Complex.

Stadler Benedek B Gorgas Nikolaus N White Andrew J P AJP Crimmin Mark R MR

Angewandte Chemie (Weinheim an der Bergstrasse, Germany) 20230309 16

Herein we present the first double deprotonation of acetonitrile (CH3CN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN]2- dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CH2CN]- complex, ...[more]

PMID: 38516673

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Project description:The knowledge of the formation of gas-phase carcinogenic acetonitrile (CH3CN) is limited in interstellar, troposphere, and combustion mediums; thus, its formation and fate are of great importance for all these gas-phase environments when accessing its toxicity and its wide range of applications. In this work, we propose a mechanism for the formation of CH3CN from the reaction of OH/O2 on ethanimine (CH3CH=NH) using ab initio/Density Functional Theory (DFT) potential energy surface in combination with microcanonical variational transition state theory (µVTST) and Ramsperger-Kassel-Marcus (RRKM)/master equation (ME) simulation to predict the rate constants and branching fraction in the temperature range of 100 K to 1000 K and pressure range of 0.0001 bar to 100 bar. The reaction starts with cis (Z) and trans (E) CH3CH=NH isomer with OH radical followed by spontaneous formation via pre-reactive complex, forming the carbon and nitrogen-centered radicals. The O2 radical then attacks the carbon and nitrogen-centered radicals to form acetonitrile (CH3CN) and HO2 radicals. The results show that N-H and C-H dominate the H-atoms abstraction by OH radicals is similar to its isoelectronic analogous reaction system, i.e., CH3CHO + OH/O2 and CH3CHCH2 + OH/O2 and similar to methanimine (CH2NH) systems. The calculated rate constants for OH-initiated oxidation of CH3CH=NH are in the range of ~ 10-11 cm3 molecule-1 s-1 (at 300 K) and are in very good agreement with previous experimental values of its isoelectronic reaction system. The atmospheric lifetime due to the loss of CH3CHNH by OH radical (10 to 11 h) is in very good agreement with the similar pollutants in the troposphere temperature range between 200 and 320 K. The results indicate that its contribution to global warming is negligible. However, the formation of products such as CH3CN may interact with other atmospheric species, which could lead to the production of potentially hazardous compounds such as cyanogen (N2C2) and hydrogen cyanide (HCN).

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Double Deprotonation of CH₃CN by an Iron-Aluminium Complex.

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Double Deprotonation of CH<sub>3</sub>CN by an Iron-Aluminium Complex.

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Double Deprotonation of CH3CN by an Iron-Aluminium Complex.

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Double Deprotonation of CH&lt;sub&gt;3&lt;/sub&gt;CN by an Iron-Aluminium Complex.

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Double Deprotonation of CH₃CN by an Iron-Aluminium Complex.

Double Deprotonation of CH<sub>3</sub>CN by an Iron-Aluminium Complex.