Hypervalente Moleküle

Musher, Jeremy I.

doi:10.1002/ange.19690810204

Cited by 147 publications

(37 citation statements)

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“…The lead atoms of 3 a and 3 b are coordinated by two THF and pyridine molecules, respectively, from above and below the plumbole rings, and the O À Pb À O and N À Pb À N angles are 175.62(6)8 and 168.41 (7)8, respectively, which are wider than the corresponding angles in Jacobs (A: 157.7(1) and 158.6(1)8) [20a] and Jurkschats (B: 149.5(1)8) [20b] compounds (Figure 3), thus suggesting that each compound has a hypervalent 10-Pb-4 structure. The PbÀO distances in 3 a are 2.6606(19) and 2.6635 (19) , which are similar to those of Joness C and Roeskys D hypervalent Pb II compounds, [20g, h] but longer than those found in Jurkschats B and Lyczkos E related compounds. [20b,f] The Pb À N distance in 3 b is 2.6877 (17) , which is similar to those of Jacobs hypervalent Pb II compounds.…”

Section: Resultsmentioning

confidence: 79%

Synthesis, Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes

Saito

Akiba

Kaneko

et al. 2013

Chemistry A European J

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Plumbacyclopentadienylidenes, in which the lead atoms have divalent states and are coordinated by THF, pyridine and N-heterocyclic carbene, were synthesized and characterized. The THF- and pyridine-stabilized compounds can be regarded as rare examples of hypervalent 10-X-4 species. The equilibrium between the THF adduct and the free plumbacyclopentadienylidene was evidenced by spectroscopic analysis and theoretical calculations. The THF adduct in benzene converted into a plumbylene dimer, where one of the lead centers is coordinated by THF and the other lead atom is coordinated by a divalent lead atom, the dimer gradually decomposing into spiroplumbole. The THF adduct unexpectedly reacted with trifluoroborane and trichlorogallane to afford fluoroborole and chlorogallole, which are the first examples of non-annulated fluoroborole and gallole, respectively.

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Section: Resultsmentioning

confidence: 79%

Synthesis, Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes

Saito

Akiba

Kaneko

et al. 2013

Chemistry A European J

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“…Encouraged by these results we have investigated the reactions of Ar 2 TeO with 2-, 3-and 4-pyridine carboxylic acids (LH). We have been able to isolate Ar 2 Te(L)(OH) (1), Ar 2 Te(L) 2 (2), Ar 2 Te(L)OTe(L)Ar 2 (3) and Ar 2 Te(L)OTe(Ar) 2 OTe(L)Ar 2 (4). The synthesis, reactivity and structural characterization of these divergent product types is discussed herein.…”

Section: Introductionmentioning

confidence: 95%

“…We were interested in investigating the corresponding reactions with organotellurium oxides to find out if divergent structural types can be formed by modulating the nature of protic acid. As part of this research activity we have recently reported the reactions of Ar 2 TeCl 2 (Ar = 4-MeO-C 6 H 4 ) with 1,1 0 -ferrocenedicarboxylic acid (L 0 H 2 ) which afforded the heterometallic macrocycle [Ar 2 TeL 0 ] 2 . [42].…”

Section: Introductionmentioning

confidence: 99%

Assembly of diverse structural types of organotellurium compounds in the reactions of (4-MeO-C6H4)2TeO with pyridine carboxylic acids

Chandrasekhar

Kumar

2009

Journal of Organometallic Chemistry

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“…Calculations are also reported for the staggered conformations of the protonation products CH3SH,+ and CH3PH3+. Thevariousgeometriesandtotalenergies of the two heavy-atom sulfur and phosphorus lThe usual equation [3], which approximates the solution to Dl, [3] Ae, = 2(A,, -eioSij)2i(eio -ero) could not be used because of the unusually large stabilizing interactions in these molecules. Can Tables 1 and 2, respectively.…”

mentioning

confidence: 99%

A theoretical study of the CSH₄ and CPH₅ hypersurfaces. Geometries, tautomerization, and dissociation of sulfonium and phosphonium ylides

Mitchell¹,

Wolfe²,

Schlegel³

1981

Can. J. Chem.

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. Can. J. Chem. 59,3280 (1981). Calculations have been performed at four basis set levels (STO-3G, STO-3G*, 4-31Ci, 4-31G*) on the model ylides rnethylenesulfurane (CH,SH,) and methylenephosphorane (CH,PH,), their stable tautomers (CH,SH and CH,PH,), their dissociation products (SH,, PH, and CH,), and the protonated species CH,SH,+ and CH,PH,+. At each basis set level all geometries have been optimized fully, using the FORCE method. The conformational behaviour of the ylides as a function of C-X bond-stretching, C-X torsion. and CH, (or SH,) bending has been examined in some detail. The experimental properties (i.e., geometries, relative stabilities, proton affinities, rotation-inversion behaviour) of sulfonium and phosphonium ylides are reproduced well by the model calculations with the 4-31G* basis set, which contains d-type functions on both carbon and sulfur (or phosphorus). All other basis sets are deficient in different ways and for different reasons, whichare discussed in detail. The principal result of this work is the conclusion that d-type functions are essential for a proper description of the hypervalent species CH,SH, and CH,PH,, but not for the normal-valent species SH,, PH,, CH,SH, and CH,PH,. The conclusion concerning hypervalent species reverses our earlier views. The role of the d-type functions is to concentrate charge into the C-X region of the ylides, and thus to stabilize the system. Evidence for this effect has been obtained from quantitative perturbational molecular orbital (PMO) analyses of interactions associated with the carbon lone pair. as well as comparisons of electron density plots with and without the d AO's. A second conclusion is that the imposition of various geometrical constraints such as assumed C-X, C-H, or X-H bond lengths, and HCH or XH, bond angles, as was necessary for computational reasons in all previous work on such systems, has major and previously unrecognized consequences. For example. the assumption that the CH, moiety is planar in CH,SH, leads to very similar geometries with and without d AO's, although only in the latter case does such a geometry at carbon correspond to the true energy minimum: in the absence of d AO's the C-S bond length is maintained by a symmetry-enforced barrier to dissociation. These and other consequences of geometrical constraints at carbon, sulfur, or phosphorus are analyzed in detail.DAVID JOHN MITCHELL, SAUL WOLFE et H . BERNHARD SCHLEGEL. Can. J. Chem. 59, 3280 (1981). Utilisant quatre ensembles de base (STO-3G, STO-3G*, 4-31G, 4-31G*), on a effectue des calculs sur des modeles d'ylures de methylenesulfurane (CH,SH,) et de methylenephophorane (CH,PH,), sur leurs tautomeres stables (CH,SH et CH,PH,), sur leurs produits de dissociation (SH,, PH, et CH,) et sur leurs especes protonees CH,SH,, CH3PH3+. Faisant appel a la methode de FORCE, on a optimise pleinement toutes les geometries pour tous les ensembles de base. On a examine soigneusement le comportement conformationnel des ylures en fonction de l'elongation de la liaison C-X, de l...

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Hypervalente Moleküle

Abstract: Salzlosung befordern [104.1061.

Cited by 147 publications

References 59 publications

Synthesis, Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes

Synthesis, Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes

Assembly of diverse structural types of organotellurium compounds in the reactions of (4-MeO-C6H4)2TeO with pyridine carboxylic acids

A theoretical study of the CSH₄ and CPH₅ hypersurfaces. Geometries, tautomerization, and dissociation of sulfonium and phosphonium ylides

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Hypervalente Moleküle

Abstract: Salzlosung befordern [104.1061.

Cited by 147 publications

References 59 publications

Synthesis, Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes

Synthesis, Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes

Assembly of diverse structural types of organotellurium compounds in the reactions of (4-MeO-C6H4)2TeO with pyridine carboxylic acids

A theoretical study of the CSH4 and CPH5 hypersurfaces. Geometries, tautomerization, and dissociation of sulfonium and phosphonium ylides

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A theoretical study of the CSH₄ and CPH₅ hypersurfaces. Geometries, tautomerization, and dissociation of sulfonium and phosphonium ylides