Selenium Imides:  77Se NMR Investigations of the SeCl2−tBuNH2 Reaction and X-ray Structures of Se3(NtBu)3, tBuNSe(μ-NtBu)2SO2, and tBuNSe(μ-NtBu)2SeO

Maaninen, Tiina; Chivers, Tristram; Laitinen, Risto S.; Schatte, Gabriele; Nissinen, Maija

doi:10.1021/ic000598b

Cited by 47 publications

(86 citation statements)

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“…[34][35][36] A similar [2+2] cycloaddition has also been observed between Se(N t Bu)2 and t BuNSeO. 37 Sandblom et al 28 have reported a DFT study of the conformations and dimerization energies of E(NMe)2 (E = S, Se, Te). 38 These calculations have verified the facile [2+2] cycloaddition of Te(NMe)2.…”

Section: -32mentioning

confidence: 76%

Conformations and Energetics of Sulfur and Selenium Diimides

et al. 2003

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The geometries and energetics of different conformations of sulfur and selenium diimides E(NR)2 (E = S, Se; R = H, Me, t Bu, C6H3Me2-2,6, SiMe3) have been studied by using various ab initio and DFT molecular orbital techniques. The syn,syn conformation is found to be most stable for parent E(NH)2 but in general the preferred molecular conformation for substituted chalcogen diimides is syn,anti. In the case of E(NH)2 the present calculations further confirm that syn,syn

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Section: -32mentioning

confidence: 76%

Conformations and Energetics of Sulfur and Selenium Diimides

et al. 2003

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“…15 Herberhold and Jellen claimed the formation of "Se3(N t Bu)2" from the decomposition of 1a, 12 but subsequent studies showed that this product is Se9(N t Bu)6. 14 This new finding suggests that the smaller oligomer [Se3(N t Bu)2]n (n = 1 or 2), which was isolated from the reaction of SeCl2 with tert-butylamine in THF, 14 is also a five-membered ring (n = 1). The structure of a related five-membered ring Se3(AsPh)2 has been reported.…”

Section: Computational Detailsmentioning

confidence: 99%

“…1-3) can be compared with the experimental values 11,14 and with the molecular parameters that have been observed for monomeric sulfur 49 and selenium diimides. 11 The calculated parameters are found to be close to the experimental values, where available:…”

Section: Cyclodimerization Of Chalcogen Diimides and Related Cycloaddmentioning

confidence: 99%

“…13 The unsymmetrical imido-oxo species t BuNSe(-N t Bu)2SeO (4a) has a cyclic structure similar to that of 2a. 14 The limited information available on cyclic selenium imides indicates the existence of a more varied series of macrocycles compared to their sulfur analogues, which are primarily limited to eight-membered rings S8-x(NH)x (x = 1-4) that are structurally related to cyclooctasulfur. 2,3 Early work by Roesky et al led to the structural characterization of the eight-membered ring Se6(N t Bu)2 and the fifteen-membered ring Se9(N t Bu)6.…”

Section: Introductionmentioning

confidence: 99%

“…14 A third product of this decomposition was identified, on the basis of analytical and spectroscopic data, as a member of the homologous series [Se3(N t Bu)2]n (n = 1 or 2). 14 We have now investigated by 77 Se NMR the thermal decomposition of 1b which leads to the novel five-membered ring 6b, in addition to the six-membered ring 5b and the partial hydrolysis products 2b and 4b. In order to rationalize the structures of the imidoselenium(V) systems 1, 2 and 4, we have also carried out high level quantum chemical calculations of the energetics for the cyclodimerization of E(NR)2 and RNEO (E = S, Se; R = H, Me, t Bu, SiMe3), and some related cycloaddition reactions.…”

Section: Introductionmentioning

confidence: 99%

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Experimental and Theoretical Investigations of Structural Trends for Selenium(IV) Imides and Oxides: X-ray Structure of Se₃(NAd)₂

et al. 2004

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The thermal decomposition of Se(NAd)2 (Ad = 1-adamantyl) in THF was monitored by 77 Se NMR and shown to give the novel cyclic selenium imide Se3(NAd)2 as one of the products. An X-ray structural determination showed that Se3(NAd)2 is a puckered five-membered ring with d(Se-Se) = 2.404(1) Å and |d(Se-N)| = 1.873(4) Å. On the basis of 77 Se NMR data other decomposition products include the six-membered ring Se3(NAd)3, and the four-membered rings AdNSe(-NAd)2SeO and OSe(-NAd)2SeO.The energies for the cyclodimerization of E(NR)2 and RNEO (E = S, Se; R = H, Me, t Bu, SiMe3), and the cycloaddition reactions of RNSeO with E(NR)2, RNSO2 with Se(NR)2, and S(NR)2 with Se(NR)2 have been calculated at MP2, CCSD and CCSD(T) levels of theory using the cc-pVDZ basis sets and B3PW91/6-31G* optimized geometries. Sulfur(IV) and selenium(IV) diimide monomers are predicted to be stable, the sole exception being Se(NSiMe3)2 that shows a tendency towards cyclodimerization. The cyclodimerization energy for the RNSeO and the cycloaddition reaction energies of RNSeO with Se(NR)2 as well as that of RNSO2 with Se(NR)2 are negative, consistent with the observed formation of OSe(-N t Bu)2SeO, OSe(-N t Bu)2SeN t Bu and O2S(-N t Bu)2SeN t Bu, respectively. Cycloaddition is unlikely when one of the reactants is a sulfur(IV) diimide.

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Selenium: Inorganic ChemistryBased in part on the article Selenium: Inorganic Chemistry by Bernt Krebs, Stefan Bonmann, & Illenora Eidenschink which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Atwood

2005

Encyclopedia of Inorganic Chemistry

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Selenium is the first member of the group 16 elements O, S, Se, Te, and Po that shows some metallic character. The increasing metallic character in the series O, S, Se, Te, Po is reflected also in the lower electronegativity, in the less acid character of the oxides, and in the lower stability of the oxidation number +VI for selenium compared to sulfur. There is a large variety of compounds of SeII, SeIV, and SeVI with the electronegative elements N, O, F, Cl, and Br. Thus, there are six general types of compounds, and these will comprise the main sections in the article. They are cations, halides, oxides, haloselenates, oxohaloselenates, and the related compounds that form when both selenium and nitrogen are present in the molecule.

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Selenium Imides: ⁷⁷Se NMR Investigations of the SeCl₂−^tBuNH₂ Reaction and X-ray Structures of Se₃(N^tBu)₃, ^tBuNSe(μ-N^tBu)₂SO₂, and ^tBuNSe(μ-N^tBu)₂SeO

Cited by 47 publications

References 37 publications

Conformations and Energetics of Sulfur and Selenium Diimides

Conformations and Energetics of Sulfur and Selenium Diimides

Experimental and Theoretical Investigations of Structural Trends for Selenium(IV) Imides and Oxides: X-ray Structure of Se₃(NAd)₂

Selenium: Inorganic ChemistryBased in part on the article Selenium: Inorganic Chemistry by Bernt Krebs, Stefan Bonmann, & Illenora Eidenschink which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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Selenium Imides: 77Se NMR Investigations of the SeCl2−tBuNH2 Reaction and X-ray Structures of Se3(NtBu)3, tBuNSe(μ-NtBu)2SO2, and tBuNSe(μ-NtBu)2SeO

Cited by 47 publications

References 37 publications

Conformations and Energetics of Sulfur and Selenium Diimides

Conformations and Energetics of Sulfur and Selenium Diimides

Experimental and Theoretical Investigations of Structural Trends for Selenium(IV) Imides and Oxides: X-ray Structure of Se3(NAd)2

Selenium: Inorganic ChemistryBased in part on the article Selenium: Inorganic Chemistry by Bernt Krebs, Stefan Bonmann, & Illenora Eidenschink which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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Selenium Imides: ⁷⁷Se NMR Investigations of the SeCl₂−^tBuNH₂ Reaction and X-ray Structures of Se₃(N^tBu)₃, ^tBuNSe(μ-N^tBu)₂SO₂, and ^tBuNSe(μ-N^tBu)₂SeO

Experimental and Theoretical Investigations of Structural Trends for Selenium(IV) Imides and Oxides: X-ray Structure of Se₃(NAd)₂