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Abstract
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.