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Quadruple bonding between iron and boron in the BFe(CO)₃^- complex.

ABSTRACT: While main group elements have four valence orbitals accessible for bonding, quadruple bonding to main group elements is extremely rare. Here we report that main group element boron is able to form quadruple bonding interactions with iron in the BFe(CO)₃^- anion complex, which has been revealed by quantum chemical investigation and identified by mass-selected infrared photodissociation spectroscopy in the gas phase. The complex is characterized to have a B-Fe(CO)₃^- structure of C_3v symmetry and features a B-Fe bond distance that is much shorter than that expected for a triple bond. Various chemical bonding analyses indicate that the complex involves unprecedented B?Fe quadruple bonding interactions. Besides the common one electron-sharing ? bond and two Fe?B dative ? bonds, there is an additional weak B?Fe dative ? bonding interaction. This finding of the new quadruple bonding indicates that there might exist a wide range of boron-metal complexes that contain such high multiplicity of chemical bonds.

SUBMITTER: Chi C

PROVIDER: S-EPMC6797760 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Quadruple bonding between iron and boron in the BFe(CO)3- complex.

Chi Chaoxian C Wang Jia-Qi JQ Hu Han-Shi HS Zhang Yang-Yang YY Li Wan-Lu WL Meng Luyan L Luo Mingbiao M Zhou Mingfei M Li Jun J

Nature communications 20191017 1

While main group elements have four valence orbitals accessible for bonding, quadruple bonding to main group elements is extremely rare. Here we report that main group element boron is able to form quadruple bonding interactions with iron in the BFe(CO)3- anion complex, which has been revealed by quantum chemical investigation and identified by mass-selected infrared photodissociation spectroscopy in the gas phase. The complex is characterized to have a B-Fe(CO)3 ...[more]

PMID: 31624260

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Project description:Transforming CO2 into valuable materials is an important reaction in catalysis, especially because CO2 concentrations in the atmosphere have been growing steadily due to extensive fossil fuel usage. From an environmental perspective, reduction of CO2 to valuable materials should be catalyzed by an environmentally benign catalyst and avoid the use of heavy transition-metal ions. In this work, we present a computational study into a novel iron(I) porphyrin catalyst for CO2 reduction, namely, with a tetraphenylporphyrin ligand and analogues. In particular, we investigated iron(I) tetraphenylporphyrin with one of the meso-phenyl groups substituted with o-urea, p-urea, or o-2-amide groups. These substituents can provide hydrogen-bonding interactions in the second coordination sphere with bound ligands and assist with proton relay. Furthermore, our studies investigated bicarbonate and phenol as stabilizers and proton donors in the reaction mechanism. Potential energy landscapes for double protonation of iron(I) porphyrinate with bound CO2 are reported. The work shows that the bicarbonate bridges the urea/amide groups to the CO2 and iron center and provides a tight bonding pattern with strong hydrogen-bonding interactions that facilitates easy proton delivery and reduction of CO2. Specifically, bicarbonate provides a low-energy proton shuttle mechanism to form CO and water efficiently. Furthermore, the o-urea group locks bicarbonate and CO2 in a tight orientation and helps with ideal proton transfer, while there is more mobility and lesser stability with an o-amide group in that position instead. Our calculations show that the o-urea group leads to reduction in proton-transfer barriers, in line with experimental observation. We then applied electric-field-effect calculations to estimate the environmental effects on the two proton-transfer steps in the reaction. These calculations describe the perturbations that enhance the driving forces for the proton-transfer steps and have been used to make predictions about how the catalysts can be further engineered for more enhanced CO2 reduction processes.

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Quadruple bonding between iron and boron in the BFe(CO)₃^- complex.

Publications

Quadruple bonding between iron and boron in the BFe(CO)<sub>3</sub><sup>-</sup> complex.

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