Baeyer–Villiger (BV) oxidation is a fundamental organic reaction, whereas the hetero-BV oxidation is uncharted. Herein, a tellura-BV oxidation is discovered. By oxidizing a tellurophene-embedded and electron-rich polycycle (1) with mCPBA or Oxone, an oxygen atom is inserted into the Te–C bond of the tellurophene to form tellurinate lactone mono-2. This reaction proceeds as follows: (i) 1 is oxidized to the tellurophene Te-oxide form (IM-1); (ii) IM-1 undergoes tellura-BV oxidation to give mono-2. Moreover, the hybrid trichalcogenasumanenes 7 and 8 are, respectively, converted to tellurinate lactones mono-9 and mono-10 under the same conditions, indicating that tellura-BV oxidation shows high chemoselectivity. Due to the strong secondary bonding interactions between the TeO groups on tellurinate lactones, mono-2, mono-9, and mono-10 are dimerized to form U-shaped polycycles 2, 9, and 10, respectively. Notably, mono-2, mono-9, mono-10, and their dimers show chirality. This work enables one-step transformation of tellurophene into tellurinate lactone and construction of intricate polycycles.

/pdf/a-tellura-baeyer-villiger-oxidation-one-step-transformation-34us29okjv.pdf

A tellura-Baeyer–Villiger oxidation: one-step transformation of tellurophene into chiral tellurinate lactone

Chalcogenide-capped triiron clusters [Fe3(CO)9(μ3-E)2], [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) as proton-reduction catalysts

Structural Variety of Iron Carbonyl Clusters Featuring Ferrocenylphosphines

Proton reduction by phosphinidene-capped triiron clusters

New iron clusters [Fe3(μ3-Q)(μ3-AsN(i-Bu)2)(CO)9] (Q = Se (1a) and Te (1b)) are synthesized. Hydrolysis reactions of these compounds that break the As-N bond are studied. The structures of clusters 1a,b and products of hydrolysis, namely [Fe6(μ6,η2-AsOAs)(μ3-Te)2(CO)18] (2), [NH2(i-Bu)2][Fe3(μ3-Se)×× (μ3-AsO)(CO)9] (3), and [{Fe3(μ3-Se)(μ4-As)(CO)9}2{Fe2(μ2-Se)2 (CO)5}] (4) are determined by the single crystal X-ray diffraction analysis.

Synthesis and Structure of [Fe3(μ3-Q)(μ3-AsN(i-Bu)2)(CO)9] (Q = Se, Te) Clusters and Products of Their Hydrolysis

Heating the 50-electron cluster [Fe3(CO)9 (μ3-Te)2] (1) with the diphosphines Ph2P-R-PPh2 [R = -CH2CH2 (dppe), Z-CH=CH (dppv), 1,2-C6H4 (dppb), -CH2CH2CH2 (dpp), ferrocenyl (dppf), naphthalenyl (dppbn)] in benzene affords the 52-electron diphosphine-containing tellurium-capped triiron clusters [Fe3(CO)8 (μ3-Te)2 (κ2-diphosphine)] (diphosphine = dppe, dppv, dppb, dpp, dppf, dppnd) (2–7) in moderate yields, resulting from both phosphine addition and carbonyl loss. With 1,2-bis(diphenylphosphino) benzene (dppb) a second product is the cubane cluster [Fe4(CO)10 (μ3-Te)4 (κ2-dppb)] (8). Cyclic voltammetry measurements on 2–7 reveals that all clusters show irreversible reductive behaviour at ca. −1.85 V with a series of associated small back oxidation waves, suggesting that reduction leads to significant structural change but that this can be reversed chemically. Oxidation occurs at relatively low potentials and is diphosphine-dependent. The first oxidation appears at ca. +0.35 V for 2–6 with a small degree of reversibility but is as low as +0.14 V for the bis(diphenylphosphino)naphthalene derivative 7 and in some cases is followed by further closely-spaced oxidation. Addition of [Cp2Fe][PF6] to 2–7 results in the formation of new clusters formulated as [Fe3(CO)8 (μ3-Te)2 (κ2-diphosphine)]+, with their IR spectra suggesting oxidation at the diiron centre. This is supported by computational studies (DFT) of the bis(diphenylphosphino)propane cluster 5 showing that the HOMO is the FeFe σ-bonding orbital, while the LUMO is centered on the diphosphine-substituted iron atom and has significant FeTe σ∗-anti-bonding character consistent with the irreversible nature of the reduction. Complexes 2–7 have been examined as proton reduction catalysts in the presence of para-toluenesulfonic acid (TsOH). All are active at their first reduction potential, with a second catalytic process being observed at slightly higher potentials. While their overall electrocatalytic behaviour is similar to that noted for the [Fe2(CO)6{μ-E (CH2)3E}] (E = S, Se, Te), the DFT results suggest that as the added electron is localised on the unique iron atom, the mechanistic aspects of hydrogen formation are likely to be quite different from the more widely studied diiron models.

Synthesis and molecular properties of the 52-electron triiron telluride clusters [Fe3(CO)8(u-Te)2(k2-diphosphine)] - Electrochemical properties and activity as proton reduction catalysts

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Synthesis and molecular properties of the 52-electron triiron telluride clusters [Fe3(CO)8(u-Te)2(k2-diphosphine)] - Electrochemical properties and activity as proton reduction catalysts