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WIREs Comput Mol Sci
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Hydrocarbon σ‐radical cations

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Abstract The structure and transformations of radical cations derived from saturated hydrocarbons in the gas phase and solution may be, in most cases, predicted with high‐level computational methods. The review covers so‐called sigma‐radical cations, i.e., the species with partially broken CH and CC bonds. The radical cations formed from the small acyclic (methane, ethanes, and butanes), as well as cyclic (cyclopropane, cyclobutane, and rotanes) and polycyclic hydrocarbons were analyzed. © 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 1 661–679 DOI: 10.1002/wcms.24 This article is categorized under: Structure and Mechanism > Molecular Structures

The structures of methane (1•+), ethane (2•+), n‐butane (3•+), and isobutane (4•+) radical cations.

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Single‐electron oxidations of diamondoids.

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The structures of selected diamondoid radical cations.

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Vertical ionization potentials (kcal/mol) of selected diamondoids at B3LYP/6–31G(d).

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The preparative oxidation of homoadamantane 22 with 1,2,4,5‐tetracyanobenzene.

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The complexation of homoadamantane radical cation 22•+ with acetonitrile.

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The pseudo‐degenerate highest occupied molecular orbitals (HOMO) and HOMO‐1 orbitals of homoadamantane 22 and the structure of the homoadamantane 22•+ radical cation optimized at B3LYP (first line) and MP2 (second line) with 6–31+G(d) basis set (bond distances in Å).

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The oxidation of protoadamantane (20) in the presence photoexcited 1,2,4,5‐tetracyanobenzene.

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The BLYP (first entries), B3LYP (second entries), and MP2 (third entries) optimized geometries of protoadamantane (20), protoadamantane radical cation (20•+), and the highest occupied molecular orbitals (HOMO) of 20. [6–31G(d), bond distances in Å].

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The possible schemes of the photoinduced SET and electrochemical oxidation of tert‐butyl adamantane.

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Optimized geometry of 1‐isopropyl‐ (18•+) and 1‐(tert‐butyl)‐ (19•+) adamantane radical cations [BLYP/6–31G(d), bond lengths are in Å]

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Optimized geometry of radical cations 17a•+ and 17b•+ and transition structure 17ab•+ [first line–BLYP/6–31G(d), second line–MP2/6–31G(d), bond lengths are in Å] of the 1‐ethyladamantane radical cation.

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Optimized geometry of radical cations 16a•+ and 16b•+ and transition structures 16ab•+ and 16c•+ [first line–BLYP/6–31G(d), second line–MP2/6–31G(d), bond lengths are in Å].

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Selective bridgehead deprotonation of the adamantane radical cation upon SET oxidation.

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The gas (left) and condensed (right) phase pathways for adamantane radical cation fragmentations [kcal/mol, B3LYP/6–31G(d) (first line), and MP2/6–31G(d) (second line)].

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Geometry of the adamantane radical cation (15•+) and transition structure of H loss (15a)[MP2/6–31G(d)], complex with water (15b), [B3LYP/6–31G(d)]. Bond lengths are in Å.

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Extended, tight, and open structures of [1.1.1.1]pagodane radical cation..

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The B3LYP/6–31G(d) optimized C8H8•+ structures relevant to the rearrangement of the cubane radical cation (9•+); relative energies in kcal/mol at BCCD(T)/cc–pVDZ//B3LYP/6–31G(d) and the rearrangement path for cubane (9) and cuneane (10) under the single‐electron transfer (SET) oxidation. Bond lengths are in Å.

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Structures of the cyclopropane (5a,b•+), cyclobutane (6a,b•+), [3]rotane (7a,b•+), and [4]rotane (8a•+) radical cations.

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