Publication Date:
2009-11-11
Description:
Compared with the enormous arsenal of catalysts used to produce organic compounds, complementary species that are able to mediate sophisticated organometallic transformations are virtually nonexistent. We found that stable N-heterocyclic carbenes (NHCs) can mediate unusual organometallic transformations in solution at room temperature. Depending on the choice of NHC initiator, stoichiometric or catalytic reactions of bis(cyclooctatetraene)iron [Fe(COT)2] ensue. The stoichiometric reaction leads to the isolation of a previously unknown mixed-valent species, featuring distinct and directly bonded Fe(0) and Fe(I) centers. In the catalytic process, three iron atoms are fused to afford the tri-iron cluster Fe3(COT)3, which is a hydrocarbon analog of Dewar's classic Fe3(CO)12 complex. The key step in both of these processes is proposed to involve the NHC's ability to induce metal-metal bond formation. These NHC-mediated reactions provide a foundation on which to develop future organometallic transformations that are catalyzed by organic species.〈br /〉〈br /〉〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2841742/" target="_blank"〉〈img src="https://static.pubmed.gov/portal/portal3rc.fcgi/4089621/img/3977009" border="0"〉〈/a〉 〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2841742/" target="_blank"〉This paper as free author manuscript - peer-reviewed and accepted for publication〈/a〉〈br /〉〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Lavallo, Vincent -- Grubbs, Robert H -- 5R01 GM31332/GM/NIGMS NIH HHS/ -- F32 GM085916/GM/NIGMS NIH HHS/ -- F32 GM085916-01/GM/NIGMS NIH HHS/ -- F32 GM085916-02/GM/NIGMS NIH HHS/ -- R01 GM031332/GM/NIGMS NIH HHS/ -- R01 GM031332-25/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 2009 Oct 23;326(5952):559-62. doi: 10.1126/science.1178919.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19900894" target="_blank"〉PubMed〈/a〉
Keywords:
Catalysis
;
Crystallization
;
Crystallography, X-Ray
;
Ferrous Compounds/*chemical synthesis/chemistry
;
Heterocyclic Compounds/*chemistry
;
Iron/*chemistry
;
Ligands
;
Methane/*analogs & derivatives/chemistry
;
Models, Chemical
;
Molecular Structure
;
Organometallic Compounds/*chemical synthesis/chemistry
;
Physicochemical Processes
;
Temperature
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
,
Chemistry and Pharmacology
,
Computer Science
,
Medicine
,
Natural Sciences in General
,
Physics
