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Formation of a diiron-(μ-η¹:η¹-CN) complex from acetonitrile solution.

ABSTRACT: The activation of C-C bonds by transition-metal complexes is of continuing interest and acetonitrile (MeCN) has attracted attention as a cyanide source with comparatively low toxicity for organic cyanation reactions. A diiron end-on μ-η¹:η¹-CN-bridged complex was obtained from a crystallization experiment of an open-chain iron-NHC complex, namely, μ-cyanido-κ²C:N-bis{[(acetonitrile-κN)[3,3'-bis(pyridin-2-yl)-1,1'-(methylidene)bis(benzimidazol-2-ylidene)]iron(II)} tris(hexafluorophosphate), [Fe₂(CN)(C₂H₃N)₂(C₂₅H₁₈N₆)₂](PF₆)₃. The cyanide appears to originate from the MeCN solvent by C-C bond cleavage or through carbon-hydrogen oxidation.

SUBMITTER: Schlachta TP

PROVIDER: S-EPMC11370999 | biostudies-literature | 2024 Sep

REPOSITORIES: biostudies-literature

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Formation of a diiron-(μ-η1:η1-CN) complex from acetonitrile solution.

Schlachta Tim P TP Sauer Michael J MJ Richter Leon F LF Kühn Fritz E FE

Acta crystallographica. Section C, Structural chemistry 20240808 Pt 9

The activation of C-C bonds by transition-metal complexes is of continuing interest and acetonitrile (MeCN) has attracted attention as a cyanide source with comparatively low toxicity for organic cyanation reactions. A diiron end-on μ-η1:η1-CN-bridged complex was obtained from a crystallization experiment of an open-chain iron-NHC complex, namely, μ-cyanido-κ2C:N-bis{[(acetonitrile-κN)[3,3'-bis(pyridin-2-yl)-1,1'-(methylidene)bis(benzimidazol-2-ylidene)]iron(II)} ...[more]

PMID: 39115534

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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).

Dataset Information

Formation of a diiron-(μ-η¹:η¹-CN) complex from acetonitrile solution.

Publications

Formation of a diiron-(μ-η<sup>1</sup>:η<sup>1</sup>-CN) complex from acetonitrile solution.

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