La résonance magnétique du <sup>77</sup>Se dans des composés organiques

Christiaens, L.; Piette, J. L.; Laitem, L.; Baiwir, Marcel; Denoel, J.; Llabrès, Gabriel

doi:10.1002/mrc.1270080706

Cited by 59 publications

(11 citation statements)

References 17 publications

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“…Purity and identity were confirmed by 1 H and 77 Se{ 1 H} NMR spectroscopy. [40] Synthesis of Ph 2 Se from 5 Cl: A solution of PhMgCl (0.432 mL, 2 m in THF, 0.866 mmol) was added to a solution of 4 Cl (0.132 g, 0.433 mmol; THF 5 mL) at À78 8C and was allowed to warm to room temperature, which resulted in a yellow slurry. The mixture was centrifuged and the solution was decanted.…”

Section: Methodsmentioning

confidence: 99%

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Lewis Base Sequestered Chalcogen Dihalides: Synthetic Sources of ChX₂ (Ch=Se, Te; X=Cl, Br)

Dutton

Farrar

Sgro

et al. 2009

Chemistry A European J

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The synthesis and comprehensive characterization of a series of base-stabilized ChX(2) (Ch = Se, Te; X = Cl, Br) is reported using aryl-substituted diazabutadiene and 2,2'-bipyridine (bipy) as the ligands. In stark contrast to free ChX(2) the complexes display excellent thermal stability. Their use as viable ChX(2) reagents that may be stored for later use is demonstrated in principle. The syntheses are simple and high-yielding from commercially available or easily synthesized reagents. The bipy complexes are exceedingly rare examples of this ubiquitous ligand being utilized within Group 16 chemistry; the Se examples are the first to be characterized by X-ray crystallography, and the Te species are only the second.

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Section: Methodsmentioning

confidence: 99%

“…The yellow Ph 2 Se eluted first and a yellow oil was recovered (0.206 g, 72 %) after removal of the solvent under vacuum. Purity and identity were confirmed by 1 H and 77 Se{ 1 H} NMR spectroscopy 40…”

Section: Methodsmentioning

confidence: 99%

Lewis Base Sequestered Chalcogen Dihalides: Synthetic Sources of ChX₂ (Ch=Se, Te; X=Cl, Br)

Dutton

Farrar

Sgro

et al. 2009

Chemistry A European J

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“…In addition, a multiplet at d = 346.4 ppm was found in the 77 Se NMR spectrum of 8Se 2 {cf. 77 Se NMR: d = 461 (PhSe-SePh), 275 ppm (MeSe-SeMe)}, [84,85] and a singlet at d = 287.5 ppm in the 125 Te NMR spectrum of 8Te 2 {cf. 125 Te NMR: d = 420 (PhTe-TePh), 264 ppm ((C 4 H 4 S)Te 2 )}.…”

Section: Reaction Of Biradicaloid 2ter With Small Molecules: Activatimentioning

confidence: 99%

Activation of Small Molecules by Phosphorus Biradicaloids

Hinz

Kuzora

Rosenthal

et al. 2014

Chemistry A European J

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The reactivity of biradicaloid [P(μ-NTer)]2 was employed to activate small molecules bearing single, double, and triple bonds. Addition of chalcogens (O2 , S8 , Sex and Tex ) led to the formation of dichalcogen-bridged P2 N2 heterocycles, except from the reaction with molecular oxygen, which gave a P2 N2 ring featuring a dicoordinated P(III) and a four-coordinated P(V) center. In formal [2πe+2πe] addition reactions, small unsaturated compounds such as ethylene, acetylene, acetone, acetonitrile, tolane, diphenylcarbodiimide, and bis(trimethylsilyl)sulfurdiimide are readily added to the P2 N2 heterocycle of the biradicaloid [P(μ-NTer)]2 , yielding novel heteroatom cage compounds. The synthesis, reactivity, and bonding of the biradicaloid [P(μ-NTer)]2 were studied in detail as well as the synthesis, properties, and structural features of all addition products.

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“…Presented in Table are the results of the benchmark calculations of 77 Se NMR chemical shifts of a representative series of diverse organoselenium open‐chain and heterocyclic compounds 1–17 against available experimental data taken from different sources for 1 , 2 , 3 and 12 , 4 , 5 , 6 , 7 , 8 and 9 , 10 , 11 , 13 , 14 , 15 , 16 , and 17 . Calculated at the GIAO‐MP2/dyall.av4z level (scheme C ), selenium isotropic absolute shielding constants were converted into 77 Se NMR chemical shifts scale referenced to dimethyl selenide ( δ , parts per million) as recommended by the International Union of Pure and Applied Chemistry using the equation δ = ( σ Me2Se − σ )/(1 − 10 −6 σ Me2Se ), where σ and σ Me2Se are the 77 Se NMR isotropic absolute shielding constants of, accordingly, the compound under consideration and dimethyl selenide calculated at the same level of theory.…”

Section: Resultsmentioning

confidence: 99%

MP2 calculation of ⁷⁷Se NMR chemical shifts taking into account relativistic corrections

Rusakov

Rusakova

Krivdin

2015

Magnetic Reson in Chemistry

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The main factors affecting the accuracy and computational cost of the Second-order Möller-Plesset perturbation theory (MP2) calculation of (77) Se NMR chemical shifts (methods and basis sets, relativistic corrections, and solvent effects) are addressed with a special emphasis on relativistic effects. For the latter, paramagnetic contribution (390-466 ppm) dominates over diamagnetic term (192-198 ppm) resulting in a total shielding relativistic correction of about 230-260 ppm (some 15% of the total values of selenium absolute shielding constants). Diamagnetic term is practically constant, while paramagnetic contribution spans over 70-80 ppm. In the (77) Se NMR chemical shifts scale, relativistic corrections are about 20-30 ppm (some 5% of the total values of selenium chemical shifts). Solvent effects evaluated within the polarizable continuum solvation model are of the same order of magnitude as relativistic corrections (about 5%). For the practical calculations of (77) Se NMR chemical shifts of the medium-sized organoselenium compounds, the most efficient computational protocols employing relativistic Dyall's basis sets and taking into account relativistic and solvent corrections are suggested. The best result is characterized by a mean absolute error of 17 ppm for the span of (77) Se NMR chemical shifts reaching 2500 ppm resulting in a mean absolute percentage error of 0.7%.

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La résonance magnétique du ⁷⁷Se dans des composés organiques

Abstract: Abstra~t-~~Se n.m.r. spectra of twenty-six organoselenium com

Cited by 59 publications

References 17 publications

Lewis Base Sequestered Chalcogen Dihalides: Synthetic Sources of ChX₂ (Ch=Se, Te; X=Cl, Br)

Lewis Base Sequestered Chalcogen Dihalides: Synthetic Sources of ChX₂ (Ch=Se, Te; X=Cl, Br)

Activation of Small Molecules by Phosphorus Biradicaloids

MP2 calculation of ⁷⁷Se NMR chemical shifts taking into account relativistic corrections

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La résonance magnétique du 77Se dans des composés organiques

Abstract: Abstra~t-~~Se n.m.r. spectra of twenty-six organoselenium com

Cited by 59 publications

References 17 publications

Lewis Base Sequestered Chalcogen Dihalides: Synthetic Sources of ChX2 (Ch=Se, Te; X=Cl, Br)

Lewis Base Sequestered Chalcogen Dihalides: Synthetic Sources of ChX2 (Ch=Se, Te; X=Cl, Br)

Activation of Small Molecules by Phosphorus Biradicaloids

MP2 calculation of 77Se NMR chemical shifts taking into account relativistic corrections

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Product

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La résonance magnétique du ⁷⁷Se dans des composés organiques

Lewis Base Sequestered Chalcogen Dihalides: Synthetic Sources of ChX₂ (Ch=Se, Te; X=Cl, Br)

Lewis Base Sequestered Chalcogen Dihalides: Synthetic Sources of ChX₂ (Ch=Se, Te; X=Cl, Br)

MP2 calculation of ⁷⁷Se NMR chemical shifts taking into account relativistic corrections