Ferrocenecarboselenoic Acid: Synthesis and Some Reactions

By oxidation of selenoacetic acid, CH3C(O)SeH, we have prepared the hitherto unknown diacetyl diselenide, [CH3C(O)Se]2. Its vibrational properties were studied experimentally, both in neat liquid (Fourier transform infrared spectroscopy and Raman) with the molecule isolated in argon matrix at low temperatures and theoretically using MP2 and B3LYP methods in combination with 6‐31+G(d), 6‐311++G(3df,3dp) or aug‐cc‐pvDZ basis sets. Analysis of Ar matrix spectra reveals a conformational equilibrium in gas phase at room temperature, which was interpreted by considering only two of the three stable rotamers predicted by our three‐dimensional potential energy surface scans. Energetic properties of three minima found theoretically were further studied in terms of donor–acceptor interactions by using natural bond orbital calculations at the same levels of theory. From this, it was possible to rationalize the conformational stability order and molecular structures by means of vicinal hyperconjugative delocalizations involving lone pairs on selenium or oxygen atoms and C=O, C–C or Se–C antibonding orbitals. The photochemistry of the compound in the argon matrix in the range between 200 and 800 nm was also investigated, revealing only one photochemical path to produce ketene, H2C=C=O, methylselane, CH3SeH, and carbonyl selenide, OCSe. Copyright © 2016 John Wiley & Sons, Ltd.

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“…More recently however, Takahashi et al . obtained the identical diselenide by reacting FcC(O)SeH with oxygen …”

Section: Introductionmentioning

confidence: 99%

“…[22] More recently however, Takahashi et al obtained the identical diselenide by reacting FcC(O)SeH with oxygen. [23] Oxidation with oxygen has been used by us to obtain the hitherto unknown aliphatic diselenides, [RC(O)Se] 2 [24,25] (refer to Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Vibrational spectra, conformational properties and argon matrix photochemistry of diacetyl diselenide, CH₃C(O)Se₂C(O)CH₃

Castaño

Romano

Salamanca

et al. 2016

J of Physical Organic Chem

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Rearrangements of Organoselenium and Organotellurium Compounds

Niyomura

Murai

2014

Patai's Chemistry of Functional Groups

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This chapter has reviewed two types of rearrangements of compounds involving seleno‐ and tellurocarbonyl groups. First, focus has been laid on the rearrangement of a proton, that is tautomerization. Several types of tautomerizations such as selone/selenol and tellone/tellurol (keto/enol type isomerization), chalcogenocarboxylic acids (selenol/selenoxo and tellurol/telluroxo isomerization), and selenoamidate/selenoimidate and telluroamidate/telluroimidate are described. The seleno‐ and tellurocarbonyl groups have generally been understood to be less stable than the corresponding carbonyl and thiocarbonyl groups. Nevertheless, in many cases, chalcogenoxo forms are readily generated. Intramolecular and intermolecular hydrogen bonds also play crucial roles in these tautomerizations. Several theoretical approaches to the tautomerizations are also introduced. Many of them are in accordance with experimental results. Second, selenium and tellurium versions of Claisen rearrangements are discussed. Seleno‐ and telluro‐ Claisen rearrangements generally precede milder than ordinary rearrangement and the sulfur version. In the rearrangement generating seleno‐ and telluoraldehdyes, these reactive species are trapped with dienes and alkenes. The availability of the rearrangement involving selenoamides and selenotihoic acid S‐esters as synthetic tools has been shown, in particular, for the construction of quaternary carbon centers. Despite these experimental developments, theoretical studies on seleno‐ and telluro‐Claisen rearrangement have yet to be achieved.

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New Polydentate Trimethylsilyl Chalcogenide Reagents for the Assembly of Polyferrocenyl Architectures

Fard¹,

Najafabadi²,

Hesari³

et al. 2014

Chemistry A European J

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A series of polychalcogenotrimethylsilane complexes Ar(CH2ESiMe3)n, (Ar = aryl; E = S, Se; n = 2, 3, and 4) can be prepared from the corresponding polyorganobromide and M[ESiMe3] (M = Na, Li). These represent the first examples of the incorporation of such a large number of reactive -ESiMe3 moieties onto an organic molecular framework. They are shown to be convenient reagents for the preparation of the polyferrocenylseleno- and thioesters from ferrocenoyl chloride. The synthesis, structures, and spectroscopic properties of the new silyl chalcogen complexes 1,4-(Me3SiECH2)2(C6Me4) (E = S, 1; E = Se, 2), 1,3,5-(Me3SiECH2)3(C6Me3) (E = S, 3; E = Se, 4) and 1,2,4,5-(Me3SiECH2)4(C6H2) (E = S, 5; E = Se, 6) and the polyferrocenyl chalcogenoesters [1,4-{FcC(O)ECH2}2(C6Me4)] (E = S, 7; E = Se, 8), [1,3,5-{FcC(O)ECH2}3(C6Me3)] (E = S, 9; E = Se, 10) and [1,2,4,5-{FcC(O)ECH2}4(C6H2)] (E = S, 11 illustrated; E = Se, 12) are reported. The new polysilylated reagents and polyferrocenyl chalcogenoesters have been characterized by multinuclear NMR spectroscopy ((1)H, (13)C, (77)Se), electrospray ionization mass spectrometry and, for complexes 1, 2, 3, 4, 7, 8, and 11, single-crystal X-ray diffraction. The cyclic voltammograms of complexes 7-11 are presented.

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Ferrocenecarboselenoic Acid: Synthesis and Some Reactions

Cited by 10 publications

References 17 publications

Vibrational spectra, conformational properties and argon matrix photochemistry of diacetyl diselenide, CH₃C(O)Se₂C(O)CH₃

Vibrational spectra, conformational properties and argon matrix photochemistry of diacetyl diselenide, CH₃C(O)Se₂C(O)CH₃

Rearrangements of Organoselenium and Organotellurium Compounds

New Polydentate Trimethylsilyl Chalcogenide Reagents for the Assembly of Polyferrocenyl Architectures

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Ferrocenecarboselenoic Acid: Synthesis and Some Reactions

Cited by 10 publications

References 17 publications

Vibrational spectra, conformational properties and argon matrix photochemistry of diacetyl diselenide, CH3C(O)Se2C(O)CH3

Vibrational spectra, conformational properties and argon matrix photochemistry of diacetyl diselenide, CH3C(O)Se2C(O)CH3

Rearrangements of Organoselenium and Organotellurium Compounds

New Polydentate Trimethylsilyl Chalcogenide Reagents for the Assembly of Polyferrocenyl Architectures

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Product

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Vibrational spectra, conformational properties and argon matrix photochemistry of diacetyl diselenide, CH₃C(O)Se₂C(O)CH₃

Vibrational spectra, conformational properties and argon matrix photochemistry of diacetyl diselenide, CH₃C(O)Se₂C(O)CH₃