Gas‐Phase Structure Determination of Dihydroxycarbene, One of the Smallest Stable Singlet Carbenes

Womack, Caroline C.; Crabtree, Kyle N.; McCaslin, Laura; Martı́nez, O.; Field, Robert W.; Stanton, John F.; McCarthy, Michael

doi:10.1002/anie.201311082

Cited by 18 publications

(13 citation statements)

References 58 publications

(180 reference statements)

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“…36 More recently, McCarthy and coworkers used a combination of microwave and millimeter wave spectroscopy for the structural determination of the gas-phase trans,cisrotamer. 40 Here, they confirmed a planar, C s symmetry structure, consistent with previous theoretical computations. Their structural results further illustrate the critical role that the second electron-donating group in HOCOH plays in making FIG.…”

Section: Introductionsupporting

confidence: 89%

Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Broderick

McCaslin

Moradi

et al. 2015

The Journal of Chemical Physics

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Singlet dihydroxycarbene (HOC̈OH) is produced via pyrolytic decomposition of oxalic acid, captured by helium nanodroplets, and probed with infrared laser Stark spectroscopy. Rovibrational bands in the OH stretch region are assigned to either trans,trans- or trans,cis-rotamers on the basis of symmetry type, nuclear spin statistical weights, and comparisons to electronic structure theory calculations. Stark spectroscopy provides the inertial components of the permanent electric dipole moments for these rotamers. The dipole components for trans, trans- and trans, cis-rotamers are (μa, μb) = (0.00, 0.68(6)) and (1.63(3), 1.50(5)), respectively. The infrared spectra lack evidence for the higher energy cis,cis-rotamer, which is consistent with a previously proposed pyrolytic decomposition mechanism of oxalic acid and computations of HOC̈OH torsional interconversion and tautomerization barriers.

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Section: Introductionsupporting

confidence: 89%

Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Broderick

McCaslin

Moradi

et al. 2015

The Journal of Chemical Physics

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“…The described results confirm that the heavier elements of Group 10 can form linear arrangements similar to that previously identified for Ni 2 C 3 . The detected palladium/platinum carbenes are amongst the smallest to be structurally characterized . There is a correspondence between the linear geometries of the MC 3 units identified herein and the linear carbon chains that are interceded by Pt/Pd atoms which are a feature of many synthetic coordination polymers .…”

Section: Figuresupporting

confidence: 86%

Highly Unsaturated Platinum and Palladium Carbenes PtC₃ and PdC₃ Isolated and Characterized in the Gas Phase

et al. 2016

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Carbenes of platinum and palladium, PtC3 and PdC3, were generated in the gas phase through laser vaporization of a metal target in the presence of a low concentration of a hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy and ab initio calculations confirm that both molecules are linear. The geometry of PtC3 was accurately determined by fitting to the experimental moments of inertia of twenty‐six isotopologues. The results are consistent with the proposal of an autogenic isolobal relationship between O, Au+, and Pt atoms.

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“…Nevertheless, prior experience of some of us for comparison of experimental results with theoretical spectroscopic parameters in C n H 2 (here n = 5, , 7, − and 9 , ) and SiC 4 H 2 isomers suggests that the percentage error for coupled-cluster values lies within 2–3% of experimental accuracy. The latter scenario has been proven for other systems as well, mentioned elsewhere in the literature. , Perhaps, by incorporating core–valence correlation, higher-order basis set effects, higher-order electron-correlation effects, and corrections from the zero-point vibrational motion, one could improve the accuracy of spectroscopic parameters. , However, it is noted here that for a system of this size, such an exercise is computationally highly demanding and not viable with our current resources. The harmonic vibrational frequencies and infrared intensities calculated at the CCSD(T)/cc-pVDZ level of theory for isomers 1–11 are given in the Supporting Information.…”

Section: Resultsmentioning

confidence: 86%

Six Low-Lying Isomers of C₁₁H₈ Are Unidentified in the Laboratory–A Theoretical Study

2021

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The potential energy surface of C 11 H 8 has been theoretically examined using density functional theory and coupled-cluster methods.The current investigation reveals that 2aHcyclopenta[cd]indene (2), 7-ethynyl-1H-indene ( 6), 4-ethynyl-1H-indene ( 7), 6-ethynyl-1H-indene (8), 5-ethynyl-1H-indene (9), and 7bH-cyclopenta[cd]indene (10) remain elusive to date in the laboratory. The puckered low-lying isomer 2 lies at 11 kJ mol 1 below the experimentally known molecule, cyclobuta[de]naphthalene (3), at the fc-CCSD(T)/cc-pVTZ//fc-CCSD(T)/cc-pVDZ level of theory. 2 lies at 35 kJ mol 1 above the thermodynamically most stable and experimentally known isomer, 1H-cyclopenta[cd]indene (1), at the same level. It is identified that 1,2-H transfer from 1 yields 2H-cyclopenta[cd]indene ( 14) and subsequent 1,2-H shift from 14 yields 2. Appropriate transition states have been identified and intrinsic reaction coordinate calculations have been done at the B3LYP/6-311+G(d,p) level of theory. Recently, 1-ethynyl-1H-indene (11) has been detected using synchrotron based vacuum ultraviolet ionization mass spectrometry. 2ethynyl-1H-indene (4) and 3-ethynyl-1H-indene (5) have been synthetically characterized in the past. While the derivatives of 7bH-cyclopenta[cd]indene (10) have been isolated elsewhere, the parent compound remains unidentified to date in the laboratory. Although C 11 H 8 is a key elemental composition in reactive intermediates chemistry and most of its isomers are having a non-zero dipole moment (µ 6 = 0), to the best of our knowledge, none of them have been characterized by rotational spectroscopy. Therefore, energetic and spectroscopic properties have been computed and the present investigation necessitates new synthetic studies on C 11 H 8 , in particular 2, 6-10, and also rotational spectroscopic studies on all low-lying isomers.

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Gas‐Phase Structure Determination of Dihydroxycarbene, One of the Smallest Stable Singlet Carbenes

Cited by 18 publications

References 58 publications

Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Highly Unsaturated Platinum and Palladium Carbenes PtC₃ and PdC₃ Isolated and Characterized in the Gas Phase

Six Low-Lying Isomers of C₁₁H₈ Are Unidentified in the Laboratory–A Theoretical Study

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Gas‐Phase Structure Determination of Dihydroxycarbene, One of the Smallest Stable Singlet Carbenes

Cited by 18 publications

References 58 publications

Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Reactive intermediates in 4He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Highly Unsaturated Platinum and Palladium Carbenes PtC3 and PdC3 Isolated and Characterized in the Gas Phase

Six Low-Lying Isomers of C11H8 Are Unidentified in the Laboratory–A Theoretical Study

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Highly Unsaturated Platinum and Palladium Carbenes PtC₃ and PdC₃ Isolated and Characterized in the Gas Phase

Six Low-Lying Isomers of C₁₁H₈ Are Unidentified in the Laboratory–A Theoretical Study