Reaction of three cyclic thioester ligands with triiron dodecacarbonyl and possible reaction mechanisms

Abstract

Three cyclic thioesters of the formula "−SCH 2 CH 2 SCO(CH 2) n −" (L 1 , n = 0; L 2 , = 1, L 3 , n = 2) and their reactions with Fe 3 (CO) 12 are reported. All the reactions produced a known diiron complex, [Fe 2 (μ-S 2 C 2 H 4)(CO) 6 ] (1), which suggested that in the reactions, cleavage of C-S bond to generate "SCH 2 CH 2 S" fragment is a common pathway for all the three ligands. In the case of ligand L 2 , a new complex 2, [Fe 2 {μ-SC 2 H 4 (SCH 2)-κ}(CO) 6 ] was isolated and structurally characterized. In the reaction of ligand L 3 , an unknown iron carbonyl product was isolated in addition to complex 1. Although its precise structure was not established due to its instability and low yield, its infrared spectrum and decomposing into complex 1 implied that the product may be a cluster with higher nuclearity. The experimental observations suggested that with the increase of the ring size of the cyclic thioester ligands, further bond cleavages were involved in the reaction in addition to that leading to complex 1.

The reaction of nonacarbonyldiiron with 8‐alkynyloxyquinolines: Alkynyl activation, cyclization via C‐N bond formation, and C‐H bond cleavage

“…Alternatively, nonacarbonyldiiron ([Fe 2 (CO) 9 ]), is also of the function of cleaving of C‐H bond 32–35 . Moreover, the reactions of the homoleptic iron carbonyl with ligands containing N/S atoms revealed that the C‐N and C‐S bond activation and formation are not uncommon, as we reported previously 19,36 …”

“…[32][33][34][35] Moreover, the reactions of the homoleptic iron carbonyl with ligands containing N/S atoms revealed that the C-N and C-S bond activation and formation are not uncommon, as we reported previously. 19,36 To extend our continual interests in iron carbonyl chemistry, herein, we report the reactions between nonacarbonyldiiron and three alkynes, which are attached to a quinoline moiety via an ether linkage. The quinoline scaffold is of interest due to its broad findings in medical chemicals.…”

Enabling Oxygen–Sulfur Exchange Reaction to Produce Semicrystalline Copolymers from Carbon Disulfide and Ethylene Oxide

“…Observation of the 3 J correlation peaks of methylene (CH 2 ) protons to the five carbonyl carbons (L1:L2:L3:L4:L5 = 27:38:8:10:17, rough estimation from peak integral) confirmed the matching of all of carbonyl structures with their 1 H NMR resonance peaks. [ 17,18,30,31 ] Carbonyl carbons of asymmetric thiocarbonate units (L 1 and L 3 ) have 3 J coupling with OCH 2  and SCH 2 . Correspondingly, protons of L 1 and L 3 showed two correlation peaks in the 1 H‐ 13 C HMBC spectrum (Figure 1), and only one correlation peak was observed for the proton of the symmetric linkages L 2 , L 4 , and L 5 .…”

Gas-Phase Conversion of 1,3-Dithiolane-2-Thione Into 1,3-Dithiolan-2-One Over Molybdenum Trioxide

“…By way of contrast, the existing methods include stoichiometric use of mercuric acetate (Challenger et al, 1953), mercuric oxide/acetic anhydride (Overberger and Bonsignore, 1958), polymer-supported selenoxide and telluroxide reagents (Hu et al, 1986), dimethyl sulfate followed by acid hydrolysis (Degani et al, 1994), epoxycyclohexane (Barbero et al, 1996) and potassium permanganate under phase transfer conditions (Aitken et al, 1997c). Compound 2 is long known to be a convenient precursor for synthesis of the useful unsaturated heterocycles 3 and 4 (Mayer and Gebhardt, 1964), and there have been various recent applications of the product 2 including as a component of the electrolyte in high-temperature batteries (Ihara et al, 2008), as a key intermediate in the chemical recycling of waste polycarbonate (Hata et al, 2003), and as a precursor for binuclear iron-sulfur carbonyl complexes (Lagadec et al, 1987; Xiao et al, 2017).…”