Electrophilic aromatic substitution reactions of arsabenzene

Chan, W. H.; Smith, Timothy W.; Taba, Kalulu M.

doi:10.1021/jo00318a012

Cited by 26 publications

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“…The difference of 7.4 kJ/mol at B3LYP level drops to 0.02 kJ/mol at the MP2 level. Hence, at MP2 level, the planar form of mono-As + is virtually a minimum with a very soft potential for the out-of-plane bending of the hydrogen attached to As 1 Selected geometric parameters of monosubstituted benzenes, (CH) 5 XH, obtained at B3LYP/6-31G* (underlined), MP2/6-31G** (bold) and MP2/6-31+G* (italics) levels.…”

Section: Resultsmentioning

confidence: 99%

A Theoretical Study of the Structures, Energetics, Stabilities, Reactivities, and Out-of-Plane Distortive Tendencies of Skeletally Substituted Benzenes (CH)₅XH and (CH)₄(XH)₂ (X = B^-, N⁺, Al^-, Si, P⁺, Ga^-, Ge, and As⁺)

and

Sastry

2001

J. Org. Chem.

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Ab initio molecular orbital theory at Hartree-Fock (HF), post-Hartree-Fock (MP2 and CCSD(T)), and the hybrid density functional theory (B3LYP) calculations were done on the mono-(CH)(5)XH and diskeletally substituted (CH)(4)(XH)(2) benzenes (X = B(-), N(+), Al(-), Si, P(+), Ga(-), Ge, and As(+)). The computed relative energies of the disubstituted isomers show interesting trends. While the ortho-isomer is the most stable for X = Ga(-), Ge, and As(+), meta was found to be the most stable for X = B(-), N(+), Al(-) and Si, and para was found to be the most stable for X = P(+). Various intricate factors that govern the relative stabilities, such as the sum of bond strengths in the twin Kekule forms, rule of topological charge stabilization (TCS), and electrostatic repulsion were critically examined. The sum of bond strengths in the twin Kekule forms was proved to be quite a successful measure in predicting the relative stability orders between ortho- and meta-/para-isomers. The rule of TCS breaks down especially in the presence of overwhelming factors such as the differences in the cumulative bond strengths of the two positional isomers; however, the stability ordering between the para- and meta-isomers is successfully predicted in most cases. The tendency for ring puckering increases a great deal especially when the substituents are from 3rd or 4th row. Extension of the popular inverse relationship between the thermodynamic stability and reactivity was found to be inapplicable for this class of compounds. The computed singlet-triplet energy differences and the chemical hardness (eta) values indicate that the skeletal substitution weakens the pi-strength of the benzenoid system and increases their reactivity.

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Section: Resultsmentioning

confidence: 99%

A Theoretical Study of the Structures, Energetics, Stabilities, Reactivities, and Out-of-Plane Distortive Tendencies of Skeletally Substituted Benzenes (CH)₅XH and (CH)₄(XH)₂ (X = B^-, N⁺, Al^-, Si, P⁺, Ga^-, Ge, and As⁺)

and

Sastry

2001

J. Org. Chem.

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“…1,1-Di- n -butyl-2-(trimethylsilyl)stannacyclohexa-2,5-diene (6). A solution containing 1-(trimethylsilyl)-1,4-pentadiyne (5.00 g, 36.8 mmol; Farchan) and dibutyltin dihydride (8.64 g, 36.8 mmol) in 18 mL of toluene was refluxed for 8 h. The toluene was then removed in vacuo, and stannacycle 6 was distilled under reduced pressure, providing a clear oil (bp 95−110 °C, 400 mTorr). Redistillation yielded 9.0 g (66%) of stannacycle 6 as a slightly air-sensitive colorless oil.…”

Section: Methodsmentioning

confidence: 99%

“…Our route (Scheme ) parallels the pathway followed by Maier, Paetzold, and Schmid in their pioneering synthesis of borabenzene−pyridine (five steps from 1,4-pentadiyne 3a, ). Treatment of commercially available 1-(trimethylsilyl)-1,4-pentadiyne with H 2 SnBu 2 in refluxing toluene generates stannacycle 6 in good yield. Exposure of 6 to BCl 3 leads to transmetalation, affording boracyclohexadiene 7 .…”

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Chemistry of Borabenzene: Efficient and General Synthesis of New Neutral Borabenzene−Ligand Complexes

et al. 1996

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“…Its UV photoelectron and electron transmission spectra show that the π-molecular orbitals of arsabenzene are those of an aromatic heterocycle. Arsabenzene also undergoes selected electrophilic aromatic substitution reactions …”

Section: Introductionmentioning

confidence: 99%

1-Arsanaphthalene. The Structure of Tricarbonyl(2-trimethylsilyl-1-arsanaphthalene)molybdenum

Fang

Kampf

2001

Organometallics

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1-Arsanaphthalene (3) and 2-trimethylsilyl-1-arsanaphthalene (4) have been prepared from the corresponding 1,4-dihydro-1,1-dimethyl-1-stannanaphthalenes 7 and 17, respectively, via an exchange reaction with AsCl 3 followed by dehydrohalogenation by DBU. Both 3 and 4 are in mobile equilibrium with their head-to-head Diels-Alder dimers. The reaction of 4 with Mo(CO) 3 (Py) 3 and BF 3 ‚OEt 2 affords Mo(CO) 3 complex 5. The crystal structure of 5 shows that the Mo(CO) 3 group is η 6 -bound to the C 5 As ring of the arsanaphthalene.

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Electrophilic aromatic substitution reactions of arsabenzene

Cited by 26 publications

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A Theoretical Study of the Structures, Energetics, Stabilities, Reactivities, and Out-of-Plane Distortive Tendencies of Skeletally Substituted Benzenes (CH)₅XH and (CH)₄(XH)₂ (X = B^-, N⁺, Al^-, Si, P⁺, Ga^-, Ge, and As⁺)

A Theoretical Study of the Structures, Energetics, Stabilities, Reactivities, and Out-of-Plane Distortive Tendencies of Skeletally Substituted Benzenes (CH)₅XH and (CH)₄(XH)₂ (X = B^-, N⁺, Al^-, Si, P⁺, Ga^-, Ge, and As⁺)

Chemistry of Borabenzene: Efficient and General Synthesis of New Neutral Borabenzene−Ligand Complexes

1-Arsanaphthalene. The Structure of Tricarbonyl(2-trimethylsilyl-1-arsanaphthalene)molybdenum

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Electrophilic aromatic substitution reactions of arsabenzene

Cited by 26 publications

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A Theoretical Study of the Structures, Energetics, Stabilities, Reactivities, and Out-of-Plane Distortive Tendencies of Skeletally Substituted Benzenes (CH)5XH and (CH)4(XH)2 (X = B-, N+, Al-, Si, P+, Ga-, Ge, and As+)

A Theoretical Study of the Structures, Energetics, Stabilities, Reactivities, and Out-of-Plane Distortive Tendencies of Skeletally Substituted Benzenes (CH)5XH and (CH)4(XH)2 (X = B-, N+, Al-, Si, P+, Ga-, Ge, and As+)

Chemistry of Borabenzene: Efficient and General Synthesis of New Neutral Borabenzene−Ligand Complexes

1-Arsanaphthalene. The Structure of Tricarbonyl(2-trimethylsilyl-1-arsanaphthalene)molybdenum

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A Theoretical Study of the Structures, Energetics, Stabilities, Reactivities, and Out-of-Plane Distortive Tendencies of Skeletally Substituted Benzenes (CH)₅XH and (CH)₄(XH)₂ (X = B^-, N⁺, Al^-, Si, P⁺, Ga^-, Ge, and As⁺)

A Theoretical Study of the Structures, Energetics, Stabilities, Reactivities, and Out-of-Plane Distortive Tendencies of Skeletally Substituted Benzenes (CH)₅XH and (CH)₄(XH)₂ (X = B^-, N⁺, Al^-, Si, P⁺, Ga^-, Ge, and As⁺)