Strong distortions in hexacarbonyldicobalt complexes by push–pull effects

Werz, Daniel B.; Bleiholder, Christian; Gleiter, Rolf; Röminger, Frank

doi:10.1016/j.jorganchem.2006.05.016

Cited by 4 publications

(8 citation statements)

References 21 publications

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“…It is interesting to note that all sulfonyl SO 2 ÐCsp bonds known in the literature [1.707 (Hu et al, 2004), 1.711 (Tykwinski et al, 1993) and 1.737 A Ê (present work)] are signi®cantly longer than reported sul®de SÐCsp bonds [mean 1.681 A Ê , standard error (SE) = 0.001, standard deviation = 0.013; Cambridge Structural Database, Version 5.27; Allen, 2002]. This observation was con®rmed by the determination and investigation of the structure of a mixed sulfonyl±thio compound, tert-butylsulfonyl-tert-butylthioethyne, (III) (Werz et al, 2006), which continues the series of (I) and (II), with another O atom absent at the same site. In that compound, the SO 2 ÐCsp bond is also longer than the SÐCsp bond [1.697 (2) and 1.684 (3) A Ê , respectively].…”

Section: Commentsupporting

confidence: 63%

“…The observed disorder of the O atoms leads to a somewhat restricted quality of the structure compared with (I) and thus prevents a detailed quantitative discussion of the results. However, we can con®dently state that, due to the observed symmetry, the torsion angle tert-butylÐSO 2 ÐSOÐ tert-butyl is 180 , and thus compound (II) is much more similar to (I) than to (III) (Werz et al, 2006).…”

Section: Commentmentioning

confidence: 88%

“…Compound (I) was obtained from bis(tert-butylsulfanyl)ethyne by oxidation with m-chloroperbenzoic acid (m-CPBA; Riera et al, 1990); it was recrystallized from chloroform. For the preparation of (II), tert-butylsulfonyl-tert-butylsulfanylethyne, (III) (Werz et al, 2006) (1.0 equivalent) was dissolved in chloroform and petroleum ether (4:1 v/v). The mixture was cooled to 273 K and a solution of m-CPBA (0.9 equivalents) in chloroform was added slowly.…”

Section: Methodsmentioning

confidence: 99%

“…Due to the symmetry of the molecule of (I), the tert-butylÐ SO 2 ÐSO 2 Ðtert-butyl torsion angle is exactly 180 . In contrast, in the mixed compound (III) (Werz et al, 2006), the tert-butylÐSO 2 ÐSÐtert-butyl torsion angle is nearly perfectly orthogonal (91.5 ). We assume electronic rather than steric reasons.…”

Section: Commentmentioning

confidence: 97%

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Bis(tert-butylsulfonyl)ethyne and 1-tert-butylsulfinyl-2-tert-butylsulfonylethyne

et al. 2006

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The title compounds are electron-poor ethynes. The structure determination of bis(tert-butylsulfonyl)ethyne, C10H18O4S2, (I), is the first of a bis-sulfonyl-substituted ethyne. The molecule is situated on a crystallographic inversion centre. The S-Csp bond [1.737 (2) A] is the longest of this type reported to date. 1-tert-Butylsulfinyl-2-tert-butylsulfonylethyne, C10H18O3S2, (II), which is basically the same as (I) minus one O atom, crystallizes isomorphous with (I). This results in a nearly equal distribution of the three O atoms over the four possible positions.

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Section: Commentsupporting

confidence: 63%

Section: Commentmentioning

confidence: 88%

Section: Methodsmentioning

confidence: 99%

Section: Commentmentioning

confidence: 97%

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Bis(tert-butylsulfonyl)ethyne and 1-tert-butylsulfinyl-2-tert-butylsulfonylethyne

et al. 2006

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“…For a more sterically equivalent “push–pull” internal alkyne, ethyl 4-(4′-methylphenylethynyl)benzoate 1d (Scheme ), PK reaction with Co 2 (CO) 6 and norbornene gave one regioisomer ( 2d ), where the electron-donating aryl group was found at the α-position and the electron-deficient aryl group at the β-position …”

Section: Introductionmentioning

confidence: 99%

Regiochemistry in Cobalt-Mediated Intermolecular Pauson–Khand Reactions of Unsymmetrical Internal Heteroaromatic Alkynes with Norbornene

et al. 2011

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The intermolecular Pauson-Khand (PK) reactions of sterically comparable (2-phenylethynyl)heteroaromatic compounds with norbornene, mediated by Co(2)(CO)(8) to give cyclopentenone products, were examined in this study. A synthetic protocol utilizing focused-microwave dielectric heating proved indispensable in the efficient synthesis of the PK cyclopentenone products. "π-Deficient" heteroaromatic substrates, e.g., 2-pyrones, and some "π-excessive" heteroaromatics such as 2- and 3-thiophene and 2-furan favor the β-position in the newly formed cyclopentenone ring. Other π-excessive heteroaromatics such as 2-pyrrole or 2-indole favor the α-position. A π-excessive 3-indole derivative gave a nearly equal mixture of regioisomers. The position of the nitrogen in pyridyl-containing alkyne substrates also affects the regiochemical outcome of the PK reaction. A 2-pyridyl alkyne, possessing a proximal nitrogen, influences the regioselectivity relative to a 4-pyridyl variant quite dramatically, favoring the β-position in the newly formed cyclopentenone ring. A 2-pyrimidylalkyne exhibits similar behavior to the 2-pyridylalkyne. Compounds that do not participate in PK reactions with norbornene include (2-phenylethynyl)imidazoles and the related benzimidazoles, which promote rapid decomposition of the in situ generated (μ(2)-alkyne)Co(2)(CO)(6) complexes. This stands in contrast with other nitrogen-containing heteroaromatics, e.g., pyrrole-, indole-, and pyrimidine-derived compounds, which effectively undergo PK reactions. Overall, the type of heteroaromatic group dramatically influences PK regioselectivity, which can in part be explained by rationalization of the current reaction mechanism, but not fully.

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Alkynes Between Main Group Elements: From Dumbbells via Rods to Squares and Tubes

Gleiter

Werz

2010

Chem. Rev.

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Introduction 4447 2. Alkynes Substituted by Elements of Main Groups I-IV (Except Carbon) 4449 2.1. Alkynes Substituted by Elements of Main Groups I and II 4449 2.1.1. Alkali and Alkali Earth Metal Derivatives of Alkynes 4449 2.1.2. Alkali and Alkali Earth Metal Carbides 4450 2.1.3. Quantum Chemical Calculations on the Metal-Alkyne Interaction of Group II Metals 4451 2.2. Alkynes Substituted by Elements of Main Group III 4451 2.

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Strong distortions in hexacarbonyldicobalt complexes by push–pull effects

Cited by 4 publications

References 21 publications

Bis(tert-butylsulfonyl)ethyne and 1-tert-butylsulfinyl-2-tert-butylsulfonylethyne

Bis(tert-butylsulfonyl)ethyne and 1-tert-butylsulfinyl-2-tert-butylsulfonylethyne

Regiochemistry in Cobalt-Mediated Intermolecular Pauson–Khand Reactions of Unsymmetrical Internal Heteroaromatic Alkynes with Norbornene

Alkynes Between Main Group Elements: From Dumbbells via Rods to Squares and Tubes

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