Synthesis of trimethylsilyl-μ-S,S′-ethylenedithiolatohexacarbonyldiiron and 1-methyl-3-trimethylsilyl-2,5-dithiacyclopentane by reaction of trimethylvinylsilane with S8 in the presence of Fe3(CO)12

Chernyshev, E. A.; Кузьмін, О. В.; Lebedev, A. V.; Gusev, A. I.; Los, M.; Alekseev, Nikolai V.; Nametkin, N. S.; Tyurin, V. D.; Krapivin, A. M.; Kubasova, N. A.; Заикин, В. Г.

doi:10.1016/0022-328x(83)80077-1

Cited by 15 publications

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“… No reaction is expected between the alkene and the sulfur in the absence of the iron carbonyl. The reaction of trimethylvinylsilane with sulfur in the presence of Fe 3 (CO) 12 gives a few percent of dithiolate diiron hexacarbonyl complex . The related reaction of Fe 3 (CO) 12 , S 8 , and 1-hexene (60 °C, 2 h) gives Fe 4 (μ-S)(μ-S 2 X)(CO) 11 ((HS) 2 X = 1,2-hexylenedithiol) in 2% yield. − Mixtures of Fe 3 (CO) 12 and S 8 even activate THF to produce traces of diiron complex derived from cis -tetrahydrofuran-2,3-dithiol. , Further illustrative of this theme (and the diligence of these workers) is the reaction of Fe 3 (CO) 12 , S 8 , and cyclohexene, which again gives a variety of products in low yields .…”

Section: Synthesis Of Diiron(i) Dithiolato Carbonyls From Iron(0) Rea...mentioning

confidence: 86%

“…The reaction of trimethylvinylsilane with sulfur in the presence of Fe 3 (CO) 12 gives a few percent of dithiolate diiron hexacarbonyl complex. 283 The related reaction of Fe 3 (CO) 12 , S 8 , and 1-hexene (60 °C, 2 h) gives Fe 4 ( μ -S)( μ -S 2 X)(CO) 11 ((HS) 2 X = 1,2-hexylenedithiol) in 2% yield. 284–286 Mixtures of Fe 3 (CO) 12 and S 8 even activate THF to produce traces of diiron complex derived from cis -tetrahydrofuran-2,3-dithiol.…”

Section: Synthesis Of Diiron(i) Dithiolato Carbonyls From Iron(0) mentioning

confidence: 99%

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Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

2016

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Virtually all organosulfur compounds react with Fe(0) carbonyls to give the title complexes. These reactions are reviewed in light of major advances over the past few decades, spurred by interest in Fe2(μ-SR)2(CO)x centers at the active sites of the [FeFe]-hydrogenase enzymes. The most useful synthetic route to Fe2(μ-SR)2(CO)6 involves the reaction of thiols with Fe2(CO)9 and Fe3(CO)12. Such reactions can proceed via mono-, di-, and triiron intermediates. The reactivity of Fe(0) carbonyls toward thiols is highly chemoselective, and the resulting dithiolato complexes are fairly rugged. Thus, many complexes tolerate further synthetic elaboration directed at the organic substituents. A second major route involves alkylation of Fe2(μ-S2)(CO)6, Fe2(μ-SH)2(CO)6, and Li2Fe2(μ-S)2(CO)6. This approach is especially useful for azadithiolates Fe2[(μ-SCH2)2NR](CO)6. Elaborate complexes arise via addition of the FeSH group to electrophilic alkenes, alkynes, and carbonyls. Although the first example of Fe2(μ-SR)2(CO)6 was prepared from ferrous reagents, ferrous compounds are infrequently used, although the Fe(II)(SR)2 + Fe(0) condensation reaction is promising. Almost invariably low-yielding, the reaction of Fe3(CO)12, S8, and a variety of unsaturated substrates results in C–H activation, affording otherwise inaccessible derivatives. Thiones and related C═S-containing reagents are highly reactive toward Fe(0), often giving complexes derived from substituted methanedithiolates and C–H activation.

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