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Facile scission of isonitrile carbon-nitrogen triple bond using a diborane(4) reagent.

ABSTRACT: Transition metal reagents and catalysts are generally effective to cleave all three bonds (one ? and two ?) in a triple bond despite its high bonding energy. Recently, chemistry of single-bond cleavage by using main-group element compounds is rapidly being developed in the absence of transition metals. However, the cleavage of a triple bond using non-transition-metal compounds is less explored. Here we report that an unsymmetrical diborane(4) compound could react with carbon monoxide and tert-butyl isonitrile at room temperature. In the latter case, the carbon-nitrogen triple bond was completely cleaved in the absence of transition metal as confirmed by X-ray crystallographic analysis, (13)C NMR spectroscopy with (13)C labelling and DFT calculations. The DFT calculations also revealed the detailed reaction mechanism and indicated that the key for the carbon-nitrogen triple-bond cleavage could be attributed to the presence of nucleophilic nitrogen atom in one of the intermediates.

SUBMITTER: Asakawa H

PROVIDER: S-EPMC4083417 | biostudies-literature | 2014 Jun

REPOSITORIES: biostudies-literature

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Facile scission of isonitrile carbon-nitrogen triple bond using a diborane(4) reagent.

Asakawa Hiroki H Lee Ka-Ho KH Lin Zhenyang Z Yamashita Makoto M

Nature communications 20140626

Transition metal reagents and catalysts are generally effective to cleave all three bonds (one σ and two π) in a triple bond despite its high bonding energy. Recently, chemistry of single-bond cleavage by using main-group element compounds is rapidly being developed in the absence of transition metals. However, the cleavage of a triple bond using non-transition-metal compounds is less explored. Here we report that an unsymmetrical diborane(4) compound could react with carbon monoxide and tert-bu ...[more]

PMID: 24967910

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Project description:The current research mainly focuses on transforming low-quality waste into value-added nanomaterials and investigating various ways of utilising them. The hydrothermal preparation of highly fluorescent N-doped carbon dots (N-CDs) was obtained from the carboxymethylcellulose (CMC) of oil palm empty fruit bunches and linear-structured polyethyleneimines (LPEI). Transmission electron microscopy (TEM) analysis showed that the obtained N-CDs had an average size of 3.4 nm. The N-CDs were monodispersed in aqueous solution and were strongly fluorescent under the irradiation of ultra-violet light. A detailed description of the morphology and shape was established using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was shown that LPEI were successfully tuned the fluorescence (PL) properties of CDs in both the intrinsic and surface electronic structures, and enhanced the quantum yield (QY) up to 44%. The obtained N-CDs exhibited remarkable PL stability, long lifetime and pH-dependence behaviour, with the excitation/emission maxima of 350/465.5 nm. Impressively, PL enhancement and blue-shifted emission could be seen with the dilution of the original N-CDs solution. The obtained N-CDs were further applied as fluorescent probe for the identification of Cu2+ in aqueous media. The mechanism could be attributed to the particularly high thermodynamic affinity of Cu2+ for the N-chelate groups over the surface of N-CDs and the fast metal-to-ligand binding kinetics. The linear relationship between the relative quenching rate and the concentration of Cu2+ were applied between 1-30 µM, with a detection limit of 0.93 µM. The fluorescent probe was successfully applied for the detection of Cu2+ in real water. Moreover, a solid-state film of N-CDs was prepared in the presence of poly (vinyl alcohol) (PVA) polymer and found to be stable even after 72-h of continuous irradiation to UV-lamp. In contrast to the aqueous N-CDs, the composite film showed only an excitation independent property, with enhanced PL QY of around 47%. Due to the strong and stable emission nature of N-CDs in both aqueous and solid conditions, the obtained N-CDs are ideal for reducing the overall preparation costs and applying them for various biological and environmental applications in the future.

Dataset Information

Facile scission of isonitrile carbon-nitrogen triple bond using a diborane(4) reagent.

Publications

Facile scission of isonitrile carbon-nitrogen triple bond using a diborane(4) reagent.

Similar Datasets

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