Structure cristalline et moléculaire du bromure d'o-formyl phénylsélényle (C7H5OSeBr)

Baiwir, Marcel; Llabrès, Gabriel; Dideberg, Otto; Dupont, L.; Piette, J. L.

doi:10.1107/s0567740875007236

Cited by 32 publications

(20 citation statements)

References 1 publication

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“…The N´´´Se separation of 2.063(3) is well within the sum of the van der Waals radii as reported by Pauling [31] [N, 1.5; Se, 2.0 ]. A similar observation has been made for the molecular structure of 2-formylbenzeneselenyl bromide [32] where the deviation of the SeÀBr bond from the phenyl plane is significantly reduced by Se´´´O interactions accompanied by an increase in the SeÀBr bond length. As in the case of 4, the SeÀBr distance of 2.631(9) is longer than the sum of the single-bond covalent radii for Se and Br (2.31 ).…”

Section: X-ray Crystallographic Studiessupporting

confidence: 77%

Intramolecular Se⋅⋅⋅N Nonbonding Interactions in Low-Valent Organoselenium Derivatives: A Detailed Study by1H and77Se NMR Spectroscopy and X-Ray Crystallography

Mugesh¹,

Panda²,

Singh³

et al. 1999

Chem. Eur. J.

124

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A series of novel low-valent organoselenium compounds stabilized by Se´´´N intramolecular interactions has been synthesized. The existence of Se´´´N nonbonding interactions was determined by 1 H and 77 Se NMR spectroscopy and X-ray crystallography. These interactions result in an apparent downfield shift of the 77 Se NMR signals; the shift values roughly correspond with the strength of the Se´´´N interaction. Single-crystal X-ray studies show that the strength of the Se´´´N interactions depends on the relative electronegativity of the group attached to the selenium and the nature of the heteroatom. These interactions lengthen the SeÀX (X Se, Cl, Br, I, CH 2 À ) bond trans to the N´´´Se bond and increase the possibility of nucleophilic attack on the selenium. In 77 Se chemical shift was attempted.

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Section: X-ray Crystallographic Studiessupporting

confidence: 77%

Intramolecular Se⋅⋅⋅N Nonbonding Interactions in Low-Valent Organoselenium Derivatives: A Detailed Study by1H and77Se NMR Spectroscopy and X-Ray Crystallography

Mugesh¹,

Panda²,

Singh³

et al. 1999

Chem. Eur. J.

124

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“…This distance is longer than the Se···O bond length (2.305 (19) reported for the ortho-substituted benzene derivative, 2-formylphenylselenenyl bromide (60). [36] This significantly higher Se···O distance may be owed to the weak donating property of the ester donor. The most interesting feature of the structure is the puckering of the aromatic ring.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

Aromatic Ring Strain in Arylselenenyl Bromides: Role in Facile Synthesis of Selenenate Esters via Intramolecular Cyclization

Selvakumar

Singh

Butcher

2010

Chemistry A European J

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The synthesis and reactivity of 2,6-disubstituted arylselenium compounds derived from 2-bromo-5-tert-butylisophthalic acid (43) are described. The syntheses of bis(5-tert-butylisophthalic acid dimethyl ester)diselenide (46) and bis(5-tert-butylisophthalic acid diisopropyl ester)diselenide (47) have been achieved by the reaction of the corresponding ester precursors with disodium diselenide. Reduction of diselenide 46 with lithium aluminum hydride affords 2,2'-bis(5-tert-butylbenzene-1,3-dimethanol)diselenide (53). Diselenides 46 and 47 exhibit intramolecular Se...O interaction. Compound 53 does not show any intramolecular Se...O interaction. The anomalous Se...O nonbonded coordination observed in the single-crystal X-ray structures of compounds 46, 47 and 53 is compared and contrasted. The corresponding selenenyl bromides 54 and 55, derived from the reaction of diselenides 46 and 47 with bromine, are quite stable in the solid state. However, they undergo hydrolysis and subsequent intramolecular cyclization upon heating or after having been kept in solution over a period of time to give the corresponding selenenate esters 56 and 57. The X-ray crystallographic study and density functional theory calculations on 54 at the B3LYP/6-31G(d) level of theory indicate a significant distortion in planarity of the aromatic ring. Glutathione peroxidase-like activities of diselenides 46 and 47 and their selenenate esters 56 and 57 have been studied both by thiophenol and bioassay methods. The very low glutathione peroxidase-like activity of the diselenides (46 and 47) and their selenenate esters (56 and 57) in the thiophenol assay is attributed to the presence of the relatively strong Se...O intramolecular interaction in the selenenyl sulfide intermediates. The interaction retards the catalytic activity through both thiol exchange and an intramolecular cyclization reaction.

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“…Therefore, weak nonbonded Se ⋅⋅⋅ X (X=heteroatom) interactions have been extensively studied due to their applications in asymmetric synthesis/catalysis,2, 3 enzyme‐mimetic reactions4 and protein engineering 5. The structural features of Se ⋅⋅⋅ O interactions were demonstrated several years ago by means of the crystal structure of 2‐formylbenzeneselenenyl bromide 6. Subsequently, Goldstein and co‐workers have demonstrated the importance of intramolecular Se ⋅⋅⋅ O interactions in the biological activity of certain selenazole nucleosides 7.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation on the Effect of Different Nitrogen Donors on Intramolecular Se⋅⋅⋅N Interactions

Sarma

Mugesh

2009

ChemPhysChem

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The effect of different donor nitrogen atoms on the strength and nature of intramolecular Se...N interactions is evaluated for organoselenium compounds having N,N-dimethylaminomethyl (dime), oxazoline (oxa) and pyridyl (py) substituents. Quantum chemical calculations on three series of compounds [2-(dime)C(6)H(4)SeX (1 a-g), 2-(oxa)C(6)H(4)SeX (2 a-g), 2-(py)C(6)H(4)SeX (3 a-g); X=Cl, Br, OH, CN, SPh, SePh, CH(3)] at the B3LYP/6-31G(d) level show that the stability of different conformers depends on the strength of intramolecular nonbonded Se...N interactions. Natural bond orbital (NBO), NBO deletion and atoms in molecules (AIM) analyses suggest that the nature of the Se...N interaction is predominantly covalent and involves nN-->sigma*(Se--X) orbital interaction. In the three series of compounds, the strength of the Se...N interaction decreases in the order 3>2>1 for a particular X, and it decreases in the order Cl>Br>OH>SPh approximately CN approximately SePh>CH(3) for all the three series 1-3. However, further analyses suggest that the differences in strength of Se...N interaction in 1-3 is predominantly determined by the distance between the Se and N atoms, which in turn is an outcome of specific structures of 1, 2 and 3, and the nature of the donor nitrogen atoms involved has very little effect on the strength of Se...N interaction. It is also observed that Se...N interaction becomes stronger in polar solvents such as CHCl(3), as indicated by the shorter r(Se...N) and higher E(Se...N) values in CHCl(3) compared to those observed in the gas phase.

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Structure cristalline et moléculaire du bromure d'o-formyl phénylsélényle (C7H5OSeBr)

Cited by 32 publications

References 1 publication

Intramolecular Se⋅⋅⋅N Nonbonding Interactions in Low-Valent Organoselenium Derivatives: A Detailed Study by1H and77Se NMR Spectroscopy and X-Ray Crystallography

Intramolecular Se⋅⋅⋅N Nonbonding Interactions in Low-Valent Organoselenium Derivatives: A Detailed Study by1H and77Se NMR Spectroscopy and X-Ray Crystallography

Aromatic Ring Strain in Arylselenenyl Bromides: Role in Facile Synthesis of Selenenate Esters via Intramolecular Cyclization

Theoretical Investigation on the Effect of Different Nitrogen Donors on Intramolecular Se⋅⋅⋅N Interactions

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