[18]Annulene put into a new perspective.

New insights into [18]annulene were gained by looking more closely at its X-ray structure, revealing a close face-to-face stacking of 3.16 Å in a herringbone-like crystal packing. Hexadehydro[18]annulene was co-crystalized in a benzene matrix, demonstrating the stabilizing role of intercalated solvent molecules in solid annulenes.

The Design of "Neutral" Carbanions with Intramolecular Charge Compensation.

Strategies to construct zwitterionic anions from the parent anions are proposed. Two principles are employed; the cationic counterpart is (a) attached as a substituent or (b) inserted as an integral part at a remote location in the assembly. The optimized geometries reveal that a striking similarity exists between the zwitterions and the respective precursor parent anion.

Bonding, aromaticity, and planar tetracoordinated carbon in Si2CH 2 and Ge 2CH 2.

Natural bond orbital (NBO) analyses and dissected nucleus-independent chemical shifts (NICS π z z ) were computed to evaluate the bonding (bond type, electron occupation, hybridization) and aromatic character of the three lowest-lying Si2CH2 (1-Si, 2-Si, 3-Si) and Ge2CH2 (1-Ge, 2-Ge, 3-Ge) isomers. While their carbon C3H2 analogs favor classical alkene, allene, and alkyne type bonding, these Si and Ge derivatives are more polarizable and can favor "highly electron delocalized"? and "non-classical"? structures. The lowest energy Si 2CH2 and Ge 2CH2 isomers, 1-Si and 1-Ge, exhibit two sets of 3-center 2-electron (3c-2e) bonding; a π-3c-2e bond involving the heavy atoms (C-Si-Si and C-Ge-Ge), and a σ-3c-2e bond (Si-H-Si, Ge-H-Ge).

Aromaticity evaluations of planar [6]radialenes.

The aromatic character of fused polycyclic systems varies with the nature of their annulated rings. Computed extra cyclic resonance energies (ECREs) reveal that the central six membered rings (6MRs) of the heterocyclic fused congeners 1-5 are "[6]radialene-like", but that the central 6MRs of triphenylene 9, coronene 10, and isocoronene 11 are "benzene-like." Comparisons with geometric (harmonic oscillator model of aromaticity, HOMA) and magnetic (nucleus independent chemical shifts, NICS) criteria illustrate the multifaceted nature of aromaticity in 1-11.

Structural isomerization of the gas-phase 2-norbornyl cation revealed with infrared spectroscopy and computational chemistry.

In an attempt to produce the 2-norbornyl cation (2NB(+)) in the gas phase, protonation of norbornene was accomplished in a pulsed discharge ion source coupled with a supersonic molecular beam. The C7H11(+) cation was size-selected in a time-of-flight mass spectrometer and investigated with infrared laser photodissociation spectroscopy using the method of "tagging" with argon. The resulting vibrational spectrum, containing sharp bands in the C-H stretching and fingerprint regions, was compared to that predicted by computational chemistry.

Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums.

Aromaticity, a highly stabilizing feature of molecules with delocalized electrons in closed circuits, is generally restricted to 'Hückel' systems with 4n+2 mobile electrons. Although the Möbius concept extends the principle of aromaticity to 4n mobile electron species, the rare known examples have complex, twisted topologies whose extension is unlikely. Here we report the realization of osmapentalenes, the first planar Möbius aromatic complexes with 16 and 18 valence electron transition metals.

Stabilization of anti-aromatic and strained five-membered rings with a transition metal.

Anti-aromatic compounds, as well as small cyclic alkynes or carbynes, are particularly challenging synthetic goals. The combination of their destabilizing features hinders attempts to prepare molecules such as pentalyne, an 8π-electron anti-aromatic bicycle with extremely high ring strain. Here we describe the facile synthesis of osmapentalyne derivatives that are thermally viable, despite containing the smallest angles observed so far at a carbyne carbon.

Oxidation of carbene-stabilized diarsenic: diarsene dications and diarsenic radical cations.

Oxidation of carbene-stabilized diarsenic, L:As-As:L [L: = :C{N(2,6-(i)Pr(2)C(6)H(3))CH}(2)] (1), with gallium chloride in a 1:4 ratio in toluene affords the dicationic diarsene complex [L:As═As:L](2+)([GaCl(4)](-))(2) (2(2+)[GaCl(4)](2)), while oxidation of 1 with GaCl(3) in a 1:2 ratio in Et(2)O yields the monocationic diarsenic radical complex [L:AsAs:L](•+)[GaCl(4)](-) (2(•+)[GaCl(4)]). Strikingly, complex 2(•+) is the first arsenic radical to be structurally characterized in the solid state. The nature of the bonding in these complexes was probed computationally and spectroscopically.

Why are S(n)N4 (n = 1-4) species "missing"? Answers in a broader theoretical context of binary S-N compounds.

Computational investigations of the thermochemical stability and kinetic persistence of binary S(x)N(y) compounds, SN(2), S(2)N(2), S(3)N(2), S(4)N(2), SN(4), S(2)N(4), S(3)N(4), and S(4)N(4), explain why some S(x)N(y) stoichiometries exist but not others. There is no direct link between the Hückel 4n + 2 π-electron count rule and the computed heats of formation (per atom) of the lowest-energy neutral S(n)N(4) (n = 1-4) isomers, but kinetic persistence often is paramount. Thus, the five lowest-energy S(2)N(4) minima at the B3LYP/6-311+G(3df) density functional theory level (A1-A5) all not only have high computed heats of formation [Δ(f)H°(0 K) > 131 kcal/mol or >22 kcal/mol/atom] but also have low dissociation barriers (less than 21.

Description of aromaticity in porphyrinoids.

Like the larger nonplanar Möbius rings, porphyrinoid aromaticity is not due primarily to the macrocyclic π conjugation of the corresponding annulene perimeters. The block-localized wave function (BLW)-derived aromatic stabilization energies (ASE) of several porphyrinoids reveal that, on a per atom basis, the appended 6π electron heterocycles of porphyrinoids confer aromaticity much more effectively than the macrocyclic 4n+2 π electron conjugations. There is no direct relationship between thermochemical stability of porphyrinoids and their macrocyclic 4n or 4n+2 π electron counts.

The 4,5,6-triphospha[3]radialene dianion: a phosphorus analogue of the deltate dianion. A NICS(0)(πzz) examination of their aromaticity.

Reduction of a 4,5,6-triphospha[3]radialene gave the corresponding isolable dianionic species. Despite having two deltate dianion-like π-electrons delocalized over the central framework, its small NICS(0)(πzz) value (only -2.2 ppm) indicates only limited aromaticity.

Carbene-stabilized beryllium borohydride.

The reaction of N-heterocyclic carbene, L:, with BeCl(2) quantitatively yields L:BeCl(2)1 (L: = :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2)). The carbene-stabilized beryllium borohydride monomer L:Be(BH(4))(2)2 is prepared by the reaction of 1 with LiBH(4). Compound 3, prepared by the reaction of 2 with Na(2)[Fe(CO)(4)]·dioxane, represents an unusual "dual reduction" of the imidazole ring (i.

Aromatic transition states in nonpericyclic reactions: anionic 5-endo cyclizations are aborted sigmatropic shifts.

The transition states (TSs) of 5-endo-dig and 5-endo-trig anionic ring closures are the first unambiguous examples of nonpericyclic reactions with TSs stabilized by aromaticity. Their five-center, six-electron in-plane aromaticity is revealed by the diatropic dissected nucleus-independent chemical shifts, -24.1 and -13.

Carbene-stabilized diphosphorus: bidentate complexation of BH2(+).

Reaction of carbene-stabilized diphosphorus, L:P-P:L (L: = :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2), 1), with excess BH(3)·THF affords the boronium salt [L:P(μ-BH(2))P:L](+)[B(2)H(7)](-), 2, which contains a three-membered P(2)B ring. When 2 is dissolved in THF, compounds 1 and 2 exist in a dynamic solution equilibrium.

Cleavage of carbene-stabilized disilicon.

Reaction of carbene-stabilized disilicon L:Si═Si:L (L: = :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2), 1) with BH(3)·THF results in facile cleavage of the silicon-silicon double bond and the formation of two quite different "push-pull" stabilized products with borane- and carbene-coordinated silylene moieties: 2, containing a parent silylene (:SiH(2)); and 3, containing a unique three-membered cyclosilylene.

A perfectly square-planar tetracoordinated oxygen in a tetracopper cluster-based coordination polymer.

A perfectly square-planar, D(4h)-symmetric, tetracoordinated oxygen has been observed in a tetracopper cluster-based coordination polymer that shows an unusual magnetic moment and ESR signal. The stabilization factor of the square-planar tetracoordinated oxygen has been revealed using DFT calculations.

A viable anionic N-heterocyclic dicarbene.

The first anionic N-heterocyclic dicarbene, polymeric [:C{[N(2,6-Pr(i)(2)C(6)H(3))](2)CHCLi(THF)}](n) 1, containing both normal (C2) and abnormal carbene (C4) centers in the same five-membered imidazole ring (III), has been prepared by lithiation of the imidazole monocarbene, :C{N(2,6-Pr(i)(2)C(6)H(3))CH}(2). The dicarbene nature of 1 was unambiguously demonstrated by the formation of the group 13 Lewis acid adducts (THF)(2)Li:C{[N(2,6-Pr(i)(2)C(6)H(3))](2)CHC(LA)}, where LA = AlMe(3) [2·(THF)(2)] and BEt(3) [3·(THF)(2)].

Successful computational modeling of isobornyl chloride ion-pair mechanisms.

Along with the directly related Wagner-Meerwein camphene hydrochloride-isobornyl chloride rearrangement, the racemization of isobornyl chloride involves intermediate carbocation-anion ion pairs; both processes have become mechanistic icons in organic chemistry. The two known racemization pathways, involving either a hydride transfer or a methyl migration, are observed to be concurrent. However, prior quantitative computational modeling has not been able to reproduce the fine kinetic balance of these processes.

Electrophile affinity: quantifying reactivity for the bromination of arenes.

Electrophile affinity (Ealpha), a recently proposed theoretical construct based on computed energies of arenium ion formation, rationalizes the substrate reactivity and regioselectivity of S(E)Ar bromination of three sets of available experimental arene data where closely related conditions had been employed uniformly. The Ealpha parameters (computed at B3LYP/6-311+G(2d,2p)) correlated very well (r = 0.987) with the partial rate factors (log f) for 18 regiospecific brominations of benzene and various methyl benzenes.

Communications: Infrared spectroscopy of gas phase C3H3+ ions: the cyclopropenyl and propargyl cations.

C(3)H(3)(+) ions produced with a pulsed discharge source and cooled in a supersonic beam are studied with infrared laser photodissociation spectroscopy in the 800-4000 cm(-1) region using the rare gas tagging method. Vibrational bands in the C-H stretching and fingerprint regions confirm the presence of both the cyclopropenyl and propargyl cations. Because there is a high barrier separating these two structures, they are presumed to be produced by different routes in the plasma chemistry; their relative abundance can be adjusted by varying the ion source conditions.

Planar hepta-, octa-, nona-, and decacoordinate first row d-block metals enclosed by boron rings.

Possible planar hypercoordinate molecules with first row d-block metal atoms in the centers of boron rings are explored comprehensively by density-functional theory (DFT) computations. Many optimized MB(n) (n = 7, 8, 9, and 10) neutral and charged clusters have local D(nh) minima, although these may not be the most stable isomers. The larger B(9) and B(10) rings are versatile in accommodating first row d-block metals, whereas the more compact B(8) ring only can enclose smaller transition metals (such as Mn, Fe, and Co) effectively.

Modeling dinitrogen activation by lithium: a mechanistic investigation of the cleavage of N2 by stepwise insertion into small lithium clusters.

Because of the inertness of molecular nitrogen, its practicable activation under mild conditions is a fundamental challenge. Nature can do it easily; chemists should be able to achieve comparable success. Lithium is exceptional among the main group elements in that it slowly reacts with N(2) at room temperature, leading finally to (NLi(3))(n), lithium nitride, a product of interest in its own right, because of its potential as a hydrogen storage medium.

The geometry and electronic topology of higher-order charged Möbius annulenes.

Higher-order aromatic charged Möbius-type annulenes have been L(k) realized computationally. These charged species are based on strips with more than one electronic half-twist, as defined by their linking numbers. The B3LYP/6-311+G(d,p) optimized structures and properties of annulene rings with such multiple half-twists (C(12)H(12)(2+), C(12)H(12)(2-), C(14)H(14), C(18)H(18)(2+), C(18)H(18)(2-), C(21)H(21)(+), C(24)H(24)(2-), C(28)H(28)(2+), and C(28)H(28)(2-)) have the nearly equal C-C bond lengths, small dihedral angles around the circuits, stabilization energies, and nucleus-independent chemical shift values associated with aromaticity.

Ab initio study of the geometry, stability, and aromaticity of the cyclic S2N3(+) cation isomers and their isoelectronic analogues.

A theoretical study of the geometries, energies, dissociation pathways, and aromaticity of the isomeric sulfur-nitrogen S(2)N(3)(+) rings reveals that the experimentally known 1,2-isomer is only stable kinetically. A rather high barrier inhibits its dissociation into the slightly lower energy N(2) and NSS(+) fragments via a stepwise mechanism. A second possible dissociation mode, into NNS and NS(+) via a concerted [3 + 2] mechanism, is endothermic.