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Title: Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Abstract

We report 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 Fe 2(μ-SR) 2(CO) x centers at the active sites of the [FeFe]-hydrogenase enzymes. The most useful synthetic route to Fe 2(μ-SR) 2(CO) 6 involves the reaction of thiols with Fe 2(CO) 9 and Fe 3(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 Fe 2(μ-S 2)(CO) 6, Fe 2(μ-SH) 2(CO) 6, and Li 2Fe 2(μ-S) 2(CO) 6. This approach is especially useful for azadithiolates Fe 2[(μ-SCH 2) 2NR](CO) 6. Elaborate complexes arise via addition of the FeSH group to electrophilic alkenes, alkynes, and carbonyls. Although the first example of Fe 2(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 Fe 3(CO) 12, S 8, and a varietymore » of unsaturated substrates results in C–H activation, affording otherwise inaccessible derivatives. Lastly, thiones and related C=S-containing reagents are highly reactive toward Fe(0), often giving complexes derived from substituted methanedithiolates and C–H activation.« less

Authors:
 [1];  [2]
  1. Sichuan University of Science & Engineering, Zigong (China). School of Chemistry and Pharmaceutical Engineering; University of Illinois at Urbana−Champaign, Urbana, IL (United States). School of Chemical Sciences
  2. University of Illinois at Urbana−Champaign, Urbana, IL (United States). School of Chemical Sciences
Publication Date:
Research Org.:
Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1466766
Grant/Contract Number:  
FG02-90ER14146
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Reviews
Additional Journal Information:
Journal Volume: 116; Journal Issue: 12; Journal ID: ISSN 0009-2665
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Yulong, and Rauchfuss, Thomas B. Synthesis of Diiron(I) Dithiolato Carbonyl Complexes. United States: N. p., 2016. Web. doi:10.1021/acs.chemrev.5b00669.
Li, Yulong, & Rauchfuss, Thomas B. Synthesis of Diiron(I) Dithiolato Carbonyl Complexes. United States. doi:10.1021/acs.chemrev.5b00669.
Li, Yulong, and Rauchfuss, Thomas B. Fri . "Synthesis of Diiron(I) Dithiolato Carbonyl Complexes". United States. doi:10.1021/acs.chemrev.5b00669. https://www.osti.gov/servlets/purl/1466766.
@article{osti_1466766,
title = {Synthesis of Diiron(I) Dithiolato Carbonyl Complexes},
author = {Li, Yulong and Rauchfuss, Thomas B.},
abstractNote = {We report 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. Lastly, thiones and related C=S-containing reagents are highly reactive toward Fe(0), often giving complexes derived from substituted methanedithiolates and C–H activation.},
doi = {10.1021/acs.chemrev.5b00669},
journal = {Chemical Reviews},
number = 12,
volume = 116,
place = {United States},
year = {Fri Jun 03 00:00:00 EDT 2016},
month = {Fri Jun 03 00:00:00 EDT 2016}
}

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