Aza- and thiaarsolidinium cations: novel structural features for carbene analogues

Burford, Neil; Parks, Trenton M.; Royan, Bruce W.; Borecka, Bozena; Cameron, T. Stanley; Richardson, John F.; Gabe, E. J.; Hynes, Rosemary C.

doi:10.1021/ja00047a024

Cited by 52 publications

(56 citation statements)

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“…Within these structures, the intra-dimer As⋯S contacts (2.423(2) Å) are comparable with the heterocyclic As-S bonds (2.181 3)-2.326 3) Å) and substantially shorter than the sum of the van der Waals radii (3.65 Å). 27 Contrary to these find-ings, we observed the corresponding salts [MeC6H3S2As]-MCl4] 3a and 3b which were prepared according to the litera-ture method could be recrystallised by slow evaporation from CH2Cl2. They were found to be isostructural with two crystal-lographically independent cation-anion pairs in the asym-metric unit with each sitting on a crystallographic mirror plane such that the cations are rigorously planar (see ESI †).…”

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confidence: 62%

Supramolecular aggregation in dithia-arsoles: chlorides, cations and N-centred paddlewheels

et al. 2017

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contrasting

confidence: 62%

Supramolecular aggregation in dithia-arsoles: chlorides, cations and N-centred paddlewheels

et al. 2017

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“…Nevertheless, the distinctly ionic structure shows no evidence of interaction between cations (shortest intercationic As-N 5.62(2) A) (Fig. 4) in contrast to the dimeric 6 structure of 4[GaC14] (as well as 3[GaC14]) (7). This implies that the association between monomers in 6 is weak, consistent with the relatively long intermonomer bonds observed in 6, and 'H NMR spectroscopic data for 4,[GaC14],, which indicate a monomer-dimer equilibrium in solution (7 .…”

Section: Resultsmentioning

confidence: 99%

“…Compounds 4CI and 4,[GaC14],, were prepared as previously reported (7). Diethyl ether was dried over sodium with benzophenone, CCl, was dried over P20,, CD,Cl, and CH2C1, were dried over P205 and CaH,, and all solvents were stored in evacuated bulbs.…”

Section: Methodsmentioning

confidence: 99%

“…Despite the identification of various arsenium cations l b (5,6), few examples have been comprehensively characterized (7), and the heavier congeneric systems l c (8,9) and l d (9,10) are rarely mentioned in the literature. The use of a Hiickel framework 2 allowed for the isolation of the first arsenium derivative (11).…”

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confidence: 99%

“…The use of a Hiickel framework 2 allowed for the isolation of the first arsenium derivative (11). However, in the absence of such charge delocalization, heterolytic As-CI bond cleavage from the chloroarsolidines 3C1 and 4C1 provided dimeric structures 6 in the solid state (7), in contrast to the phospholidinium 7 analogue (2). We present here the preparation and structures of the sixmembered diazarsenane 5C1 and the tetrachlorogallate salt of the corresponding diazarsenanium cation 5, which is clearly monomeric in the solid state.…”

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Preparation and structure of 2-chloro-1,3-dimethyldiaza-2-arsenane, 1,3-dimethyldiaza-2-arsenanium tetrachlorogallate, and butadiene cycloadducts of diazarsenium cations

Burford¹,

Macdonald²,

Parks³

et al. 1996

Can. J. Chem.

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1,3-Dimethyldiaza-2-arsenanium tetrachlorogallate (crystal data: C5H12AsC14GaN2, M = 386.61, orthorhombic, space group P~a 2~, a = 14.432(3) A, b = 6.7580(14) A, c = 13.905(3) A, V = 1356.2(5) A3) is synthesized by the routine chloride ion abstraction procedure from 2-chloro-l,3-dimethyldiaza-2-arsenane (crystal data: C5H,,AsC1N2, M = 210.54, monoclinic, space group P21/n, a = 7.206(1) A, b = 9.650(1) A, c = 13.021(2) A, P = 99.61(2)', V = 892.8(2) A3). X-ray crystallographic studies of both compounds are described together with that for 2-chloro-l,3-dimethyldiaza-2-arsolidine (crystal data: C4HloAsC1N2, M = 196.51, monoclinic, space group P2,ln, a = 6.959(7) A, b = 9.23(2) A, c = 12.14(2) A, P = 95.4(1)', V = 777(4) A3) providing useful structural comparisons. In contrast to the closely related arsolidinium salts, the diazarsenanium gallate exhibits a monomeric solid state structure. Rapid and quantitative cycloaddition reactions of the diazarsolidinium and diazarsenanium cations with 2,4-dimethylbutadiene give similar cycloadducts. The Diels-Alder type arsolidinium adduct is structurally characterized (crystal data: Cl,H20AsC14GaN2, M = 454.73, orthorhombic, space group Pca2,, a = 18.47 l(2) A, b = 7.000(2) A, c = 13.738(1) A, V = 1776.2(8) A3), and the related structure of the arsenanium cycloadduct is confirmed by 2D NMR. IKey words: arsenium, cycloadditions, arsenanium, Diels-Alder, cyclochloroarsines. (2) A, p = 95,4(1)', V = 777(4) A3). Par opposition aux structures trbs apparentCes des sels d'arsolidinium, le gallate de diazarsknanium prksente une structure monomCrique i 1'Ctat solide. Des reactions de cycloadditions rapides et quantitatives des cations diazarsolidinium et diazarsknanium avec le 2,4-dimCthylbutadibne conduisent i des cycloadduits semblables. On a caractCrisC la structure de l'adduit de type Diels-Alder du cation arsolidinium (donnCes cristallographiques : CloH20AsC14GaN2, M = 454,73, orthorhombique, groupe d'espace Pca2,, a = 18,471(2), b = 7,000(2) et c = 13,738(1) A, V = 1776,2(8) A3) et on a confirm6 la structure apparentCe du cycloadduit du cation arsCnanium par RMN en 2D.

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Cation Stabilities, Electrophilicities, and “Carbene Analogue” Character of Low Coordinate Phosphorus Cations

Gudat

1998

Eur. J. Inorg. Chem.

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The stabilities of low coordinated phosphorus cations can be expressed in the frame of the HSAB concept by the transferred charge density Δq(N) which a cation receives upon formation of a donor‐acceptor adduct with a Lewis base N. This concept allows to differentiate between relative stabilities towards different reaction partners, and to compare the electrophilicities of phosphenium ions to those of isoelectronic carbenes and silylenes. An analysis of substituent influences on Δq(H) in cations [P(R)2]+suggests an increasing stabilizing power of substituents in the series R = Cl < CH3 < OH, SH < NH2. The same ordering was derived from isodesmic hydride transfer reactions. Interpretation of population analyses suggests that the individual substituent contributions to cation stabilities result from a balance between π‐donation into the empty p(P) orbital and electrostatic stabilization by polar P–R σ‐bonds. A further stabilizing effect, which is of similar magnitude as in isoelectronic carbenes or silylenes, may arise from cyclic π‐conjugation between a diaminophosphenium fragment and an adjacent double bond. Substituent effects influence further the nature of the frontier orbitals of phosphenium ions, resulting in orbital sequences which resemble those of carbenes, allyl anions, or phospholides, respectively. The absence of frontier orbital related changes in reactivity patterns suggests that in all reactions, including metal complex formation, phosphenium ions behave as purely electrophilic rather than ambiphilic species.

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Aza- and thiaarsolidinium cations: novel structural features for carbene analogues

Cited by 52 publications

References 3 publications

Supramolecular aggregation in dithia-arsoles: chlorides, cations and N-centred paddlewheels

Supramolecular aggregation in dithia-arsoles: chlorides, cations and N-centred paddlewheels

Preparation and structure of 2-chloro-1,3-dimethyldiaza-2-arsenane, 1,3-dimethyldiaza-2-arsenanium tetrachlorogallate, and butadiene cycloadducts of diazarsenium cations

Cation Stabilities, Electrophilicities, and “Carbene Analogue” Character of Low Coordinate Phosphorus Cations

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