Synthesis of (diphosphine)Ni-bridged double-butterfly Fe/S cluster complexes and isolation of the reactive μ-CO-containing anionic Fe/S cluster intermediates

Song, Li‐Cheng; Li, Ling; Hu, Yuanyuan; Song, Haibin

doi:10.1016/j.jorganchem.2013.06.043

Cited by 8 publications

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“…These anions are prepared by the reaction of Fe 3 (CO) 12 with thiolate anions, often in the form of the mixture RSH/Et 3 N (eq ). − The formulas for these monothiolato diiron(0) species are sometimes more explicitly written as [Fe 2 (μ-SR)(μ-CO)(CO) 6 ] − , which highlights their structural similarity to Fe 2 (μ-SR) 2 (CO) 6 . The salts Et 3 NH[Fe 2 (μ-SR)(CO) 7 ] convert to the diiron(I) dithiolates, usually in low yields, upon heating − and with weak oxidants and electrophiles. − These diiron(0) anions are oxidized by S 8 to give what are proposed to be diiron(I) anions.…”

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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