Bis(tert-butyl)sulfurdiimide, S(NBut)2, and tris(tert-butyl)sulfurtriimide, S(NBut)3: structures by gas electron diffraction, X-ray crystallography and ab initio calculations

Hinchley, Sarah L.; Trickey, P.; Robertson, Heather E.; Smart, Bruce A.; Rankin, David W. H.; Leusser, Dirk; Walfort, Bernhard; Bühl, Michæl; Obrey, Stephen J.

doi:10.1039/b207193b

Cited by 18 publications

(10 citation statements)

References 52 publications

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“…117.4(2)8 in tBu-NSN-tBu]. [100] None of the species considered here displayed any significantly shorter intermolecular distances. Hence, only weak van der Waals interactions between the molecules can be assumed.…”

Section: Structure Elucidation Of P 2 N 2 Cage Compoundsmentioning

confidence: 77%

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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Section: Structure Elucidation Of P 2 N 2 Cage Compoundsmentioning

confidence: 77%

Activation of Small Molecules by Phosphorus Biradicaloids

Hinz

Kuzora

Rosenthal

et al. 2014

Chemistry A European J

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“…intermolekulare Wasserstoffbrücken sind unmöglich, da das N1(H)‐Wasserstoffatom nicht dem freien Elektronenpaar an N2 zugewandt ist. Die Imido‐Bindungslänge von S1‐N2 mit 1.5273(3) Å und die Amido‐Bindungslänge von S1‐N1 mit 1.6482(3) Å stimmen sehr gut mit bereits in der Gasphase [22, 23] und mit hochaufgelösten Röntgendaten im Festkörper bestimmten Längen in S(N t Bu) 3 ( 2 ), [19] S(N t Bu) 2 ( 3 ) [20] und CH 2 {S(N t Bu) 2 (NH t Bu)} 2 ( 4 ) [21] überein (Tabelle 1). Zur Klärung der Ladungsdichteverteilung in 1 und vor allem der Bindungssituation der unterschiedlichen S‐N‐Bindungen, die entscheidend für das Verhalten der Einzelmolekülmagnete (SMMs) ist, wurden eine Multipolverfeinerung nach dem Hansen‐und‐Coppens‐Modell [24] und eine auf der Quantum Theory of Atoms in Molecules (QTAIM) basierende topologische Analyse [25] durchgeführt.…”

Section: Methodsunclassified

Tetraimidoschwefelsäure H₂S(NtBu)₄– isovalenzelektronisch zu H₂SO₄

2021

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Das zur Schwefelsäure H2SO4 isovalenzelektronische Imido‐Analogon H2S(NtBu)4 wurde synthetisiert, isoliert und mittels NMR‐Spektroskopie sowie hochaufgelöster Röntgenstrukturanalyse und Ladungsdichteuntersuchungen charakterisiert. Letzteres zeigt stark polarisierte Sδ+‐Nδ−‐Bindungen mit praktisch keinem Doppelbindungscharakter. Die leicht zu polarisierenden S‐N‐Bindungen sind eine vorteilhafte und vielseitige Eigenschaft der Schwefel‐Stickstoff‐Liganden, mit der sie sich unterschiedlichen elektronischen Anforderungen verschiedener Metallkationen anpassen können.

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“…1st row to 2nd row p-block bond lengths have been found to be particularly difficult to determine using ab initio techniques. [18] Eur. J. Inorg.…”

Section: Structural Comparisonsmentioning

confidence: 98%

Causes of Nonplanarity in Fluorinated 1,3λ⁴δ²,2,4‐Benzodithiadiazines: Gas‐Phase Electron Diffraction, Ab initio and DFT Structures

et al. 2005

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The gas‐phase molecular structures of 6,8‐difluoro‐1,3λ4δ2,2,4‐benzodithiadiazine and 5,6,7‐trifluoro‐1,3λ4δ2,2,4‐benzodithiadiazine have been determined using quantum chemical calculations and electron diffraction via the SARACEN method of structural analysis. Of particular interest was the planarity or nonplanarity of the heterocyclic fragments of the molecules. It was shown that the difluoro compound is planar with respect to the heterocyclic fragment [folding angle: 0.0(5)° (figures in parenthesis indicate e.s.d.s in the final digits)] and that the trifluoro compound probably deviates from planarity to a small extent [folding angle: 4.0(−30;+3)°; the large uncertainty in the value of this angle is due to the low‐frequency, large‐amplitude vibrational motion associated with the folding of the heterocyclic fragment]. Pertinent structural parameters from the electron diffraction data (rh1 structure) of the difluoro compound are av[r(S=N)] = 155.7(7) pm, r(S−N) = 175.8(5) pm, r(C−S) = 176.6(8) pm and r(C−N) = 141.6(2) pm. For the trifluoro compound the equivalent structural parameters are av[r(S=N)] = 155.5(7) pm, r(S−N) = 170.7(6) pm, r(C−S) = 180.6(8) pm and r(C−N) = 140.6(2) pm. The gas‐phase electron diffraction structures have been compared with results from ab initio and DFT calculations and also with experimental solid‐state structures. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Bis(tert-butyl)sulfurdiimide, S(NBut)2, and tris(tert-butyl)sulfurtriimide, S(NBut)3: structures by gas electron diffraction, X-ray crystallography and ab initio calculations

Cited by 18 publications

References 52 publications

Activation of Small Molecules by Phosphorus Biradicaloids

Activation of Small Molecules by Phosphorus Biradicaloids

Tetraimidoschwefelsäure H₂S(NtBu)₄– isovalenzelektronisch zu H₂SO₄

Causes of Nonplanarity in Fluorinated 1,3λ⁴δ²,2,4‐Benzodithiadiazines: Gas‐Phase Electron Diffraction, Ab initio and DFT Structures

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Bis(tert-butyl)sulfurdiimide, S(NBut)2, and tris(tert-butyl)sulfurtriimide, S(NBut)3: structures by gas electron diffraction, X-ray crystallography and ab initio calculations

Cited by 18 publications

References 52 publications

Activation of Small Molecules by Phosphorus Biradicaloids

Activation of Small Molecules by Phosphorus Biradicaloids

Tetraimidoschwefelsäure H2S(NtBu)4– isovalenzelektronisch zu H2SO4

Causes of Nonplanarity in Fluorinated 1,3λ4δ2,2,4‐Benzodithiadiazines: Gas‐Phase Electron Diffraction, Ab initio and DFT Structures

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Tetraimidoschwefelsäure H₂S(NtBu)₄– isovalenzelektronisch zu H₂SO₄

Causes of Nonplanarity in Fluorinated 1,3λ⁴δ²,2,4‐Benzodithiadiazines: Gas‐Phase Electron Diffraction, Ab initio and DFT Structures