Two cumulene carbenes, H2C5 and H2C6, were detected in a supersonic molecular beam by Fourier transform microwave spectroscopy. Their rotational and leading centrifugal distortion constants were determined with high accuracy, such that the entire radio spectrum can now be calculated. Like the known carbenes H2C3 and H2C4, both molecules have singlet electronic ground states and linear carbon-chain backbones. They can be produced in sufficiently high concentrations in the laboratory that their electronic spectra, expected to lie in the visible, should be readily detectable by laser spectroscopy. The microwave spectra of other, more exotic isomers may be detectable as well.
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http://dx.doi.org/10.1126/science.275.5299.518 | DOI Listing |
Angew Chem Int Ed Engl
May 2024
School of Chemical Science and Engineering, Tongji University, 1239 Siping Rd, Shanghai, China, 200092.
Cyanoketene is a fundamental molecule that is actively being searched for in the interstellar medium. Its deprotonated form (cyanoketenate) is a heterocumulene that is isoelectronic to carbon suboxide whose structure has been the subject of debate. However, the investigation of cyanoketene and its derivatives is hampered by the lack of practical synthetic routes to these compounds.
View Article and Find Full Text PDFOrg Biomol Chem
February 2024
Universität Potsdam, Institut für Chemie, Karl-Liebknecht-Str. 24-25, D-14476 Potsdam(Golm), Germany.
The spatial magnetic properties, particularly the through-space NMR shieldings (TSNMRSs, the anisotropy effect in H NMR spectroscopy) of carbenes, carbones and carbodication (carbo2+) compounds (with and without stabilization by NMe π-donation) and those of a number of carbo2+ analogues have been calculated using the GIAO perturbation method, employing the nucleus-independent chemical shift (NICS) concept, and visualized as iso-chemical-shielding surfaces (ICSS) of various sizes and directions. TSNMRSs prove the electronic structure of carbo2+ compounds to be completely different from those of carbenes and carbones, preferring both the π-electron distribution and the structure of allenes/cumulenes despite the central carbon atom being the most electrophilic centre.
View Article and Find Full Text PDFJ Am Chem Soc
January 2024
Department of Chemistry, University of California, Berkeley, California 94720, United States.
Alkylidene cyclopropanes (ACPs) are valuable synthetic intermediates because of their constrained structure and opportunities for further diversification. Although routes to ACPs are known, preparations of ACPs with control of both the configuration of the cyclopropyl ( vs ) group and the geometry of the alkene ( vs ) are unknown. We describe enzymatic cyclopropanation of allenes with ethyl diazoacetate (EDA) catalyzed by an iridium-containing cytochrome (Ir(Me)-CYP119) that controls both stereochemical elements.
View Article and Find Full Text PDFJ Org Chem
October 2023
Department of Chemistry, Colby College, Waterville, Maine 04901, United States.
Photolysis of 1-(2-adamantylidene)-1a,9b-dihydro-1-cyclopropa[]phenanthrene in benzene (or benzene-) at ambient temperature produces adamantylidenecarbene. The carbene undergoes dimerization to a cumulene and may also be trapped in a stereospecific fashion by - and -4-methyl-2-pentene. No products attributable to 4-homoadamantyne, resulting from ring expansion of the carbene, could be detected.
View Article and Find Full Text PDFMolecules
September 2023
School of Science and Technology, University of New England, Armidale, NSW 2351, Australia.
We evaluate the accuracy of CCSD(T) and density functional theory (DFT) methods for the calculation of equilibrium rotational constants (Ae, Be, and Ce) for four experimentally detected low-lying C5H2 isomers (ethynylcyclopropenylidene (), pentatetraenylidene (), ethynylpropadienylidene (), and 2-cyclopropen-1-ylidenethenylidene ()). The calculated rotational constants are compared to semi-experimental rotational constants obtained by converting the vibrationally averaged experimental rotational constants (A0, B0, and C0) to equilibrium values by subtracting the vibrational contributions (calculated at the B3LYP/jun-cc-pVTZ level of the theory). The considered isomers are closed-shell carbenes, with cumulene, acetylene, or strained cyclopropene moieties, and are therefore highly challenging from an electronic structure point of view.
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