An ab initio study on the equilibrium structure and CCC bending energy levels of carbon suboxide

Koput, Jacek

doi:10.1016/s0009-2614(00)00237-2

Cited by 70 publications

(69 citation statements)

References 29 publications

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“…The model also nicely explains why the gas-phase value [21] for the C-C-C bond angle in carbon suboxide C 3 O 2 , which is usually written in terms of double bonds O=C=C=C=O, deviates from the value which is found in the solid state (1808) [22] and why it has a very shallow bending potential for the OC-C-CO bending mode. [21,23] It is very difficult to explain with the Lewis bonding model why carbon suboxide is not linear.…”

Section: Introductionmentioning

confidence: 99%

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Takagi

Tonner

Frenking

2012

Chemistry A European J

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Quantum-chemical calculations at the BP86/TZVPP level have been carried out for the heavy Group 14 homologues of carbodiphosphorane E(PPh(3))(2), where E=Si, Ge, Sn, Pb, which are experimentally unknown so far. The results of the theoretical investigation suggest that the tetrelediphosphoranes E(PPh(3))(2) (1E) are stable compounds that could become isolated in a condensed phase. The molecules possess donor-acceptor bonds Ph(3)P→E←PPh(3) to a bare tetrele atom E, which retains its four valence electrons as two electron lone pairs. The analysis of the bonding situation and the calculation of the chemical reactivity indicate that the molecules 1E belong to the class of divalent E(0) compounds (ylidones). All molecules 1C-1Pb have very large first but also very large second proton affinities, which distinguishes them from the N-heterocyclic carbene homologues, in which the donor atom is a divalent E(II) species that possesses only one electron lone pair. Compounds 1E are powerful double donors that strongly bind Lewis acids such as BH(3) and AuCl in the complexes 1E(BH(3))(n) and 1E(AuCl)(n) (n=1, 2). The bond dissociation energies (BDEs) of the second BH(3) and AuCl molecules are only slightly less than the BDE of the first BH(3) and AuCl. The results of this work are a challenge for experimentalists.

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Section: Introductionmentioning

confidence: 99%

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Takagi

Tonner

Frenking

2012

Chemistry A European J

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“…[4,5] We also calculated complexes of AuCl with carbon suboxide, C 3 O 2 [29] (6), as ligand, which is usually written with double bonds O=C=C=C=O. [29b,c] It has been shown that carbon suboxide, which has a quasi-linear equilibrium geometry with a remarkably shallow bending potential, [30] may also be seen as carbodicarbonyl C(CO) 2 .…”

Section: Introductionmentioning

confidence: 99%

Distinguishing Carbones from Allenes by Complexation to AuCl

Esterhuysen

Frenking

2011

Chemistry A European J

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Quantum chemical calculations have been performed for the dicoordinated carbon compounds C(PPh(3))(2), C(NHC(Me))(2), R(2) C=C=CR(2) (R = H, F, NMe(2)), C(3)O(2), C(CN)(2)(-) and N-methyl-substituted N-heterocyclic carbene (NHC(Me)). The geometries of the complexes in which the dicoordinated carbon molecules bind as ligands to one and two AuCl moieties have been optimized and the strength and nature of the metal-ligand interactions in the mono- and diaurated complexes were investigated by means of energy decomposition analysis. The goal of the study is to elucidate the differences in the chemical behavior between carbones, allenes and carbenes. The results show that carbones bind one and two AuCl species in η(1) fashion, whereas allenes bind them in η(2) fashion. Compounds with latent divalent carbon(0) character can coordinate in more than one way, with the dominant mode indicating the degree of carbone or allene character. The calculated structures of the mono- and diaurated tetraaminoallenes (TAAs) reveal that TAAs exhibit a chameleon-like behavior: The bonding situation in the equilibrium structure is best described as allene [(R(2)N)(2)]C=C=C[(NR(2))(2)] in which the central carbon atom is a tetravalent C(IV) species, but the reactivity suggests that TAAs should be considered as divalent C(0) compounds C{C[(NR(2))(2)]}(2), that is, as "hidden" carbones. Carbon suboxide binds one AuCl preferentially in the η(1) mode, whereas the equilibrium structures of the η(1)- and η(2)-bonded diaurated complex are energetically nearly degenerate. The doubly negatively charged isoelectronic carbone C(CN)(2)(2-) binds one and two AuCl very strongly in characteristic η(1) fashion. The N-heterocyclic carbene complex, [NHC(Me)(AuCl)], possesses a high bond dissociation energy (BDE) for the splitting off of AuCl. The diaurated NHC adduct, [NHC(Me)(AuCl)(2)], has two η(1)-bonded AuCl moieties that exhibit aurophilic attraction, which yield a moderate bond strength that might be large enough for synthesizing the complex. The BDE for the second AuCl in [NHC(Me)(AuCl)(2)] is clearly smaller than the values for the second AuCl in doubly aurated carbone complexes.

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“…The structure of C 3 O 2 (IUPAC: propadiene-1,3-dione) is a quasi-linear cumulene, O = C = C = C = O, with a shallow W shape which readily deforms by bending vibrations and a weak dipole moment (Karyakin et al, 1982;Winnewisser et al, 2006). Experimental and theoretical work has considered the photochemical properties of this molecule (Bayes, 1961;Smith et al, 1966;Masiello et al, 2005;Vander Auwera et al, 1991), as well as its thermodynamic and chemical properties (Winnewisser et al, 2006;McDougall and Kilpatrick, 1965;Koput, 2000;Ramasami, 2007;Kolbanovskii et al, 2014), and carbon suboxide has found some uses in organic synthesis (Kappe and Ziegler, 1974) and polymers (Carofiglio et al, 1986). It has also been shown to occur as an intermediate in abiotic degradation of aromatics in soils (Huber et al, 2007).…”

Section: Introductionmentioning

confidence: 99%

Atmospheric chemistry, sources and sinks of carbon suboxide, C<sub>3</sub>O<sub>2</sub>

et al. 2017

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Abstract. Carbon suboxide, O = C = C = C = O, has been detected in ambient air samples and has the potential to be a noxious pollutant and oxidant precursor; however, its lifetime and fate in the atmosphere are largely unknown. In this work, we collect an extensive set of studies on the atmospheric chemistry of C 3 O 2 . Rate coefficients for the reactions of C 3 O 2 with OH radicals and ozone were determined as k OH = (2.6 ± 0.5) × 10 −12 cm 3 molecule −1 s −1 at 295 K (independent of pressure between ∼ 25 and 1000 mbar) and k O 3 < 1.5 × 10 −21 cm 3 molecule −1 s −1 at 295 K. A theoretical study on the mechanisms of these reactions indicates that the sole products are CO and CO 2 , as observed experimentally. The UV absorption spectrum and the interaction of C 3 O 2 with water (Henry's law solubility and hydrolysis rate constant) were also investigated, enabling its photodissociation lifetime and hydrolysis rates, respectively, to be assessed.The role of C 3 O 2 in the atmosphere was examined using in situ measurements, an analysis of the atmospheric sources and sinks and simulation with the EMAC atmospheric chemistry-general circulation model. The results indicate sub-pptv levels at the Earth's surface, up to about 10 pptv in regions with relatively strong sources, e.g. influenced by biomass burning, and a mean lifetime of ∼ 3.2 days. These predictions carry considerable uncertainty, as more measurement data are needed to determine ambient concentrations and constrain the source strengths.

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An ab initio study on the equilibrium structure and CCC bending energy levels of carbon suboxide

Cited by 70 publications

References 29 publications

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Distinguishing Carbones from Allenes by Complexation to AuCl

Atmospheric chemistry, sources and sinks of carbon suboxide, C<sub>3</sub>O<sub>2</sub>

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An ab initio study on the equilibrium structure and CCC bending energy levels of carbon suboxide

Cited by 70 publications

References 29 publications

Carbodiphosphorane Analogues E(PPh3)2 with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Carbodiphosphorane Analogues E(PPh3)2 with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Distinguishing Carbones from Allenes by Complexation to AuCl

Atmospheric chemistry, sources and sinks of carbon suboxide, C&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt;

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Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Carbodiphosphorane Analogues E(PPh₃)₂ with E=C–Pb: A Theoretical Study with Implications for Ligand Design

Atmospheric chemistry, sources and sinks of carbon suboxide, C<sub>3</sub>O<sub>2</sub>