[μ-3-(Methylsulfanyl)benzene-1,2-dithiolato-1:2κ4S,S′:S,S′]bis[tricarbonyliron(I)]

Yang, Yong; Wang, Ning; Chen, Lin

doi:10.1107/s1600536813009860

Cited by 2 publications

(1 citation statement)

References 8 publications

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“…Because disulfides also react with iron carbonyls to give the same dithiolates, their involvement in typical syntheses would not be noticed in many preparations. The RSH/Fe 3 (CO) 12 reaction is currently the most popular route for diiron dithiolato carbonyls. ,,,− The RSH/Fe 2 (CO) 9 route to Fe 2 (μ-SR) 2 (CO) 6 is also widely employed; these reactions proceed typically at slightly lower efficiency than the Fe 3 (CO) 12 route …”

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

confidence: 99%

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

confidence: 99%

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

2016

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Iron(I)‐Based Carbonyl Complexes with Bridging Thiolate Ligands as Light‐Triggered CO Releasing Molecules (photoCORMs)

Suchland

Malassa

Görls

et al. 2019

Zeitschrift anorg allge chemie

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A series of thiolate ligands were used to synthesize diiron(I) hexacarbonyl bis(thiolates) for structural studies. Conversion of the corresponding thiols with triiron(0) dodecacarbonyl yields complexes of the type [{(CO)3Fe(μ‐SR)}2] [R = C6H5 (1), C6H4‐4‐CH3 (2), C6H4‐4‐F (3), C6F5 (4), C6H4‐4‐CF3 (5), C6H2‐2,4,6‐(CH3)3 (6), CH2–C6H4‐4‐Cl (7)]. These complexes were isolated and fully characterized, including X‐ray crystal structures of complexes 2–7. The bridging thiolate ligands mainly influence the Fe–CO bond which is trans‐positioned to the second iron(I) center. In solution, the anti‐isomer with one axially and one equatorially oriented thiolate is the major species; severe steric strain induced by mesityl groups only allows the formation of syn‐endo‐isomeric molecules of 7. Furthermore, light‐induced CO release at solid material at the three representative complexes 1, 3, and 6 verify suitability as photoCORMs.

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[μ-3-(Methylsulfanyl)benzene-1,2-dithiolato-1:2κ⁴S,S′:S,S′]bis[tricarbonyliron(I)]

Cited by 2 publications

References 8 publications

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Iron(I)‐Based Carbonyl Complexes with Bridging Thiolate Ligands as Light‐Triggered CO Releasing Molecules (photoCORMs)

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