THE REACTION OF C5H5Co(CO)2WITH MeO2CC[tbnd]CCO2Me IN THE PRESENCE OF ELEMENTAL SELENIUM: MOLECULAR STRUCTURE OF 2,3,4,5,- TETRAKIS (METHOXYCARBONYL) SELENOPHENE

Dorrity, M. R. J.; Malone, John F.; Morley, Christopher P.; Vaughan, Richard R.

doi:10.1080/10426509208038369

Cited by 10 publications

(3 citation statements)

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“…It is based on a selenophene ring which is perfectly planar [mean deviation from the C(5)C(4)C(1)C(2)Se(1) least-squares plane = 0.0049 Å], and also C(11), C(7), N(1), and C(3) lie in the same plane [maximum deviation from the plane = 0.1437 Å]. A similar situation was previously observed in SeC 4 (CO 2 Me) 4 . Alternating double and single C–C bonds are present in the ring of 5a , thus C(5)–C(4) [1.368(2) Å] and C(1)–C(2) [1.387(2) Å] are considerably shorter than C(4)–C(1) [1.439(2) Å].…”

Section: Resultssupporting

confidence: 62%

“…A similar situation was previously observed in SeC 4 (CO 2 Me) 4 . 31 Alternating double and single C−C bonds are present in the ring of 5a, 32 thus C( 5 16) Å] and C(2)−Se(1) [1.8653( 16) Å] distances are as expected for single C(sp 2 )−Se bonds. Carboxylic and carbonylic centers C (11), C(7), and C(3) display a perfect sp 2 hybridization [sum angles are 360.0(3)°], whereas N(1) presents a considerable pyramidilization [sum angle at N(1) 346.7(3)°].…”

Section: ■ Introductionmentioning

confidence: 75%

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Tetrasubstituted Selenophenes from the Stepwise Assembly of Molecular Fragments on a Diiron Frame and Final Cleavage of a Bridging Alkylidene

et al. 2020

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A series of 2,3-dicarboxylato-5-acetyl-4-aminoselenophenes, 5a – j , was obtained via the uncommon assembly of building blocks on a diiron platform, starting from commercial [Fe 2 Cp 2 (CO) 4 ] through the stepwise formation of diiron complexes [ 2a – d ]CF 3 SO 3 , 3a – d , and 4a – j . The selenophene-substituted bridging alkylidene ligand in 4a – j is removed from coordination upon treatment with water in air under mild conditions (ambient temperature in most cases), affording 5a – j in good to excellent yields. This process is highly selective and is accompanied by the disruption of the organometallic scaffold: cyclopentadiene (CpH) and lepidocrocite (γ-FeO(OH)) were identified by NMR and Raman analyses at the end of one representative reaction. The straightforward cleavage of the linkage between a bridging Fischer alkylidene and two (or more) metal centers, as observed here, is an unprecedented reaction in organometallic chemistry: in the present case, the carbene function is converted to a ketone which is incorporated into the organic product. DFT calculations and electrochemical experiments were carried out to give insight into the release of the selenophene-alkylidene ligand. Compounds 5a – j were fully characterized by elemental analysis, mass spectrometry, IR, and multinuclear NMR spectroscopy and by X-ray diffraction and cyclic voltammetry in one case.

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Section: Resultssupporting

confidence: 62%

Section: ■ Introductionmentioning

confidence: 75%

Tetrasubstituted Selenophenes from the Stepwise Assembly of Molecular Fragments on a Diiron Frame and Final Cleavage of a Bridging Alkylidene

et al. 2020

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“…Treatment of cyclopentadienyldicarbonylcobalt 152 with DMAD in toluen at reflux, in the presence of elemental selenium produce three products from which selenophene 153 (Scheme 60) [158]. MeO2 …”

Section: Cycloadditionmentioning

confidence: 99%

Synthesis of Selenophenes

Sommen

2005

MROC

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Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCV. Transition‐Metal‐Mediated Cyclocotrimerization of Selenophosphinites with Activated Alkynes

et al. 1996

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Selenophosphinito complexes (OC)4Mn(η2‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PR21) (2a, b) [R1 = cyc‐Hex (a), tBu (b)] are formed by the reaction of BrMn(CO)5 with the phosphane selenides R21HPSe (1a, b) in the presence of the auxiliary base Et(iPr)2N. According to an X‐ray structural analysis, 2a crystallizes in the space group \documentclass{article}\pagestyle{empty}\begin{document}$ P\bar 1 $\end{document} with Z = 2. The dimeric complex [(OC)4Mn(μ‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2)]2 (4c) is not obtained in a straightforward way. Compound 4c is only obtained via the intermediate Br(OC)4Mn–Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}P(H)Me2 (3c) by HBr elimination with nBuLi. Complex 3c is formed by replacement of carbon monoxide in BrMn(CO)5 by Me2HPSe (1c). A dissociative equilibrium between [(OC)4 Mn(μ‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2)]2 (4c) and the monomeric species (OC)4Mn(\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}2‐Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2) was not observed. The cyclocotrimerization of the >P\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}Se function with the activated alkynes ZCCZ [Z = CO2R2; R2 = Me (d), Et (e), iPr (f), cyc‐Hex (g)] was successful only in the case of the cyclohexyl derivative 2a to give the selenaphosphamanganabicycloheptadienes 5d – g. An X‐ray structural analysis proved that 5d crystallizes in the space group \documentclass{article}\pagestyle{empty}\begin{document}$ P\bar 1 $\end{document} with Z = 2. Under CO pressure 5d was degraded to the selenophene 6.

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THE REACTION OF C₅H₅Co(CO)₂WITH MeO₂CC[tbnd]CCO₂Me IN THE PRESENCE OF ELEMENTAL SELENIUM: MOLECULAR STRUCTURE OF 2,3,4,5,- TETRAKIS (METHOXYCARBONYL) SELENOPHENE

Cited by 10 publications

References 11 publications

Tetrasubstituted Selenophenes from the Stepwise Assembly of Molecular Fragments on a Diiron Frame and Final Cleavage of a Bridging Alkylidene

Tetrasubstituted Selenophenes from the Stepwise Assembly of Molecular Fragments on a Diiron Frame and Final Cleavage of a Bridging Alkylidene

Synthesis of Selenophenes

Preparation, Properties, and Reactions of Metal‐Containing Heterocycles, XCV. Transition‐Metal‐Mediated Cyclocotrimerization of Selenophosphinites with Activated Alkynes

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