Structure and photoelectron spectrum of 3,3'-bicyclopropenyl

Boese, Roland; Blaeser, D.; Gleiter, Rolf; Pfeifer, Karl Heinz; Billups, W. E.; Haley, Michael M.

doi:10.1021/ja00055a052

Cited by 30 publications

(8 citation statements)

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“…3,3-Bicyclopropenyl ( 70 ) is probably the least stable of the known four valence isomers of benzene . It was prepared by Billups and Haley in 1989, and its structure in the crystalline state was determined by X-ray analysis . In the same paper, its electronic structure was investigated by PE spectroscopy and quantum chemical computations.…”

Section: 51 Compounds With Two Three-membered Rings and Small Polycyc...mentioning

confidence: 99%

Photoelectron Spectra of Cyclopropane and Cyclopropene Compounds

Rademacher

2003

Chem. Rev.

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Aryl-2-(4-pyridyl)-cyclopropanes 970 3.6.8 Cyclopropylamines 970 3.6.9 Cyclopropenyl−Metal Complexes 971 4. Electronic Structure and Reactivity of Cyclopropane Compounds 971 4.1 Intramolecular Rearrangements Involving Cyclopropane Rings 971 4.2 Anchimeric Assistance of Solvolytic Reactions of 7-Norbornyl Derivatives 971 4.3 Cycloaddition Reactions 971 4.4 Radical Reactions of Bicyclo[1.1.0]butanes 972 4.5 Conclusion 972 5. Conclusions and Outlook 972 6. Acknowledgment 972 7. Note Added after ASAP Posting 972 8. References 972

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Section: 51 Compounds With Two Three-membered Rings and Small Polycyc...mentioning

confidence: 99%

Photoelectron Spectra of Cyclopropane and Cyclopropene Compounds

Rademacher

2003

Chem. Rev.

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“…The bicyclopropenyl hydrocarbon (CH) 6 8 is known to have the trans C 2h structure, 18 and indeed, the N6 analog has a minimum energy in this same conformation. One can imagine this structure as having lone pairs of electrons trans to each other at either end of the central N-N bond.…”

Section: Calculationsmentioning

confidence: 99%

Strain Energies in Homoatomic Nitrogen Clusters N₄, N₆, and N₈

Gimarc

Zhao

1996

Inorg. Chem.

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Strain energies and resonance energies can be obtained as the energy changes for appropriate homodesmotic reactions using ab initio calculated total energies as the energies of the reactants and products involved. Homodesmotic reactions conserve bond types and preserve valence environments at all atoms, requirements that favor the cancellation of basis set and electron correlation errors in the ab initio energies. In this paper we calculate strain energies and resonance energies for N(4), N(6), and N(8) clusters in a number of chemically significant but, for nitrogen, hypothetical structural forms. The nitrogen cluster strain energies are generally of the same order of magnitude as those of isostructural hydrocarbon clusters, and individual differences can be explained by using the ring strain additivity rule and recognizing the effect of the presence of lone pairs of electrons on nitrogen clusters but not on the hydrocarbons. Resonance energies of the nitrogen clusters are much smaller than those of the comparable aromatic hydrocarbons. The differences can be rationalized by considering the relative strengths of CC and NN single and double bonds. Strain and resonance energies of nitrogen clusters are compared with those previously reported for homoatomic clusters of phosphorus and arsenic. Trends through the series are remarkably similar, but strain energies for clusters from lower periods are progressively smaller. Strain and resonance have been important organizing concepts in organic chemistry for many years. Estimates of corresponding parameters for inorganic analogs are only now becoming available.

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“…In addition to the valence isomers of benzene, several other isomers, both cyclic and acyclic, exist and are interesting in their own right. − Exploration of the structural limitations in organic chemistry is an inspiring and challenging arena, which warrants a judicious combination of experiment and theory. Several experimental studies have been reported on the rearrangements of acyclic isomers of C 6 H 6 in generating other acyclic and cyclic isomeric structures. − Prominently, the rearrangement of 1,5-hexadiyne to other isomeric forms of C 6 H 6 has been the interest for more than three decades. − ,− Huntsman and Wristers have synthesized 3,4-dimethylenecyclobutene, a monocyclic isomer, in high yield from 1,5-hexadiyne by thermal cyclization at 350 °C, which was reported to occur via 1,2,4,5-hexatetraene .…”

Section: Introductionmentioning

confidence: 99%

Exploration of C₆H₆ Potential Energy Surface: A Computational Effort to Unravel the Relative Stabilities and Synthetic Feasibility of New Benzene Isomers

2004

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Ab initio (MP2, CCSD(T)) and hybrid density functional theory (B3LYP) calculations with up to triple-ζ basis set were done to locate all possible minima, where each carbon in the molecule is tetracoordinate, on the C6H6 potential energy surface. The search was initiated with a total of 218 structures, and in few cases, geometrical and stereoisomers were considered. The exhaustive study on all these topological structures resulted in a total of 263 stationary points on the C6H6 potential energy surface. The B3LYP level characterizes 209 as minima, 31 as transition states, 8 as second-order, 7 as third-order, and 1 as fourth-order saddle points. The remaining 7 structures could be located as stationary points only at the MP2 level. The molecules were classified into acyclic, monocyclic, bicyclic, tricyclic, and tetracyclic. The acyclic isomers fall within a range of 60−80 kcal/mol higher in energy compared to benzene. Among the cyclic structures, the range of relative stabilities of minima is larger, viz., monocyclic (31−146 kcal/mol), bicyclic (72−159 kcal/mol), tricyclic (72−300 kcal/mol), and tetracyclic (102−156 kcal/mol). Strain due to small three and four membered rings and constrained double and triple bonds control the relative stabilities of these isomers. The computed isomers exhibit various novel bonding modes for carbon, namely, planar tetracoordinate, hypervalent, pyramidal, bent/twisted double bonds, vicinal dicarbenes, nonlinear triple bonds, and so forth. Absolute chemical hardness values have no correlation with the relative stabilities, and about 45 molecules have higher hardness values than that of benzene.

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Structure and photoelectron spectrum of 3,3'-bicyclopropenyl

Cited by 30 publications

References 1 publication

Photoelectron Spectra of Cyclopropane and Cyclopropene Compounds

Photoelectron Spectra of Cyclopropane and Cyclopropene Compounds

Strain Energies in Homoatomic Nitrogen Clusters N₄, N₆, and N₈

Exploration of C₆H₆ Potential Energy Surface: A Computational Effort to Unravel the Relative Stabilities and Synthetic Feasibility of New Benzene Isomers

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Structure and photoelectron spectrum of 3,3'-bicyclopropenyl

Cited by 30 publications

References 1 publication

Photoelectron Spectra of Cyclopropane and Cyclopropene Compounds

Photoelectron Spectra of Cyclopropane and Cyclopropene Compounds

Strain Energies in Homoatomic Nitrogen Clusters N4, N6, and N8

Exploration of C6H6 Potential Energy Surface: A Computational Effort to Unravel the Relative Stabilities and Synthetic Feasibility of New Benzene Isomers

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Strain Energies in Homoatomic Nitrogen Clusters N₄, N₆, and N₈

Exploration of C₆H₆ Potential Energy Surface: A Computational Effort to Unravel the Relative Stabilities and Synthetic Feasibility of New Benzene Isomers