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diiron nonacarbonyl : ウィキペディア英語版
diiron nonacarbonyl

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Diiron nonacarbonyl is an inorganic compound with the formula Fe2(CO)9. This metal carbonyl is an important reagent in organometallic chemistry and of occasional use in organic synthesis.〔Elschenbroich, C.; Salzer, A. ”Organometallics : A Concise Introduction” (2nd Ed) (1992) Wiley-VCH: Weinheim. ISBN 3-527-28165-7〕 It is a more reactive source of Fe(0) than Fe(CO)5 and less dangerous to handle because it is nonvolatile. This micaceous orange solid is virtually insoluble in all common solvents.
==Synthesis and structure==
Following the original method, photolysis of an acetic acid solution of Fe(CO)5 produces Fe2(CO)9 in good yield:〔King, R. B. Organometallic Syntheses. Volume 1 Transition-Metal Compounds; Academic Press: New York, 1965. ISBN 0-444-42607-8.〕
:2 Fe(CO)5 → Fe2(CO)9 + CO
Fe2(CO)9 consists of a pair of Fe(CO)3 centers linked by three bridging CO ligands. Although older textbooks show an Fe-Fe bond consistent with the 18 electron rule (8 valence electrons from Fe, two each from the terminal carbonyls, one each from the bridging carbonyls and one from the other Fe atom in the metal-metal bond), theoretical analyses have consistently indicated the absence of a direct Fe-Fe bond:〔Jennifer C. Green, Malcolm L. H. Green, Gerard Parkin "The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds" Chem. Commun. 2012, 11481-11503. 〕 this latter model proposes an Fe-C-Fe three-center-two-electron "banana bond" for one of the bridging carbonyls. The minor isomer has been crystallized together with C60. The iron atoms are equivalent and octahedral molecular geometry. Elucidation of the structure of Fe2(CO)9 proved to be challenging because its low solubility inhibits growth of crystals. The Mößbauer spectrum reveals one quadrupole doublet, consistent with the D3h-symmetric structure.

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