(Diene)iron tricarbonyl

In organometallic chemistry, (diene)iron tricarbonyl describes a diverse family of related coordination complexes consisting of a diene ligand coordinated to a Fe(CO)3 center. Often the diene is conjugated, e.g., butadiene, but the family includes nonconjugated dienes as well. The compounds are yellow, air-stable, often low-melting, and soluble in hydrocarbon solvents. The motif is so robust that even unstable dienes form easily characterized derivatives, such as norbornadienone and cyclobutadiene.PATAI'S Chemistry of Functional Groups Organoiron Compounds The Chemistry of Diene–Iron and Dienyl–Iron Complexes Ingmar Bauer, Hans‐Joachim Knölker 2013 Wiley & Sons 10.1002/9780470682531.pat0652 Scope thumb|structure of the Fe(CO)3 adduct of vitamin A aldehyde.10.1039/J19700001229 Crystal and molecular structure of (Vitamin-A aldehyde)tricarbonyliron 1970 Mason R. Robertson G. B. Journal of the Chemical Society A: Inorganic, Physical, Theoretical 1229 The inventory of complexes is large. Receiving particular attention are complexes of linear conjugated 1,3-dienes and cyclic dienes with various spacings of the two alkene units around the ring. + Selected (diene)Fe(CO)3 Complexes Diene CAS RN Physical propertiesNotes (Butadiene)Fe(CO)3 12078-32-9 yellow-orange, m.p. 19 °Cmajor prototype(Cyclobutadiene)Fe(CO)3 12078-17-0 orange solid, b.p. 47 °C (3 mmHg)antiaromatic ligandR. Pettit J. Henery 10.15227/orgsyn.050.0021 free Cyclobutadieneiron Tricarbonyl Organic Syntheses 1970 50 21 (1,3-Cyclohexadiene)Fe(CO)312252-72-6 yellow, m.p. 8–9 °Cmajor prototype for steroidal and terpenoid derivativesCyclohexadieneiron Tricarbonyl Anthony J. Pearson Huikai Sun 2008 10.1002/047084289X.rn00791 e-EROS Encyclopedia of Reagents for Organic Synthesis 978-0471936237 (1,3-Cyclooctadiene)Fe(CO)3 33270-50-7 yellow, m.p. 36 °Cisomeric with 1,5-cyclooctadiene derivative10.1021/ja00747a066 Tricarbonyl(cyclooctadiene) Complexes of Iron(0), Ruthenium(0), and Osmium(0) 1971 Lewis J. Cotton F. A. Deeming A. J. Josty P. L. Ullah S. S. Domingos A. J. P. Johnson B. F. G. Journal of the American Chemical Society 93 18 4624–4626 (1,5-Cyclooctadiene)Fe(CO)3 12093-20-8 yellow, m.p. 76 °Cnon-conjugated diene10.1039/DT9740002093 Reactivity of co-ordinated ligands. Part XX. Preparation and Reactions of Cyclo-octadiene Complexes of Iron, Ruthenium, and Osmium 1974 Deeming A. J. Ullah S. S. Domingos A. J. P. Johnson B. F. G. Lewis J. Journal of the Chemical Society, Dalton Transactions 19 2093 10.1021/ic50166a041 Intramolecular Rearrangement in (.eta.-diene)tricarbonyliron and -Ruthenium Compounds. A Carbon-13 Nuclear Magnetic Resonance Study 1976 Kruczynski Leonard. Takats Josef. Inorganic Chemistry 15 12 3140–3147 (Isoprene)Fe(CO)3 32731-93-4 yellow liquidchiral10.1016/0022-1902(61)80495-8 Chemistry of the Metal Carbonyls—IX. Diene Complexes of Iron 1961 King R. B. Manuel T. A. Stone F. G. A. Journal of Inorganic and Nuclear Chemistry 16 3–4 233–239 (Methoxy-1,3-cyclohexadiene)Fe(CO)3 yellow oil, b.p. 66–68 °C (0.1 mmHg) Mixture of two isomers, from Birch reduction of anisole Arthur Birch (organic chemist) 1977 Birch A. J. Chamberlain K. B. Tricarbonyl[(2,3,4,5-η)-2,4-Cyclohexadien-1-one]iron and Tricarbonyl[(1,2,3,4,5-η)-2-Methoxy-2,4-Cyclohexadien-1-yl]Iron(1+) Hexafluorophosphate(1−) from Anisole 57 107 10.15227/orgsyn.057.0107 (Norbornadiene)Fe(CO)3 12307-07-2 yellow, m.p. −2 °Cnon-conjugated diene10.1039/JR9600000989 206. Spectroscopic Studies of Some Organoiron Complexes 1960 Green M. L. H. Pratt L. Wilkinson G. Journal of the Chemical Society (Resumed) 989 (Norbornadienone)Fe(CO)312307-01-6 yellow, m.p. 93–95 °Cfree diene-one is unstable10.1021/ja00733a032 Synthesis and Chemistry of Tricarbonyl(7-norbornadienone)iron 1971 Landesberg Joseph M. Sieczkowski J. Journal of the American Chemical Society 93 4 972–980 (Thebaine)iron tricarbonyl Birch A. J. Fitton H. McPartlin Mary Mason R. The structure and some reactions of the iron tricarbonyl complex of thebaine Chemical Communications (London) 1968 9 531 10.1039/C19680000531 (η4-Thiepine)Fe(CO)3-yellow, , m.p. 54.5–55 °C chiral; stable, even though free thiepine is not10.1021/ja00013a051 Thiepine-iron tricarbonyl: Stabilization of thermally labile parent thiepine by transition metal complexation 1991 Nishino Keitaro Takagi Masanobu Kawata Teruhisa Murata Ichiro Inanaga Junji Nakasuji Kazuhiro Journal of the American Chemical Society 113 13 5059–5060 (Xylylene)Fe(CO)3, m.p. 39 °Cyellow free diene is unstable10.1016/S0040-4039(00)91011-6 o-Chinodimethan - und 2. 2-Dimethyl-iso-inden-eisen-tricarbonyl 1967 Roth W.R Meier J.D Tetrahedron Letters 8 22 2053–2058 Preparation and uses Many of diene complexes were originally prepared by reaction of iron pentacarbonyl with the diene under UV-radiation: Fe(CO)5 + diene -> (diene)Fe(CO)3 + 2 CO In some cases, isolated yields are modest because the complexes, which are often liquids, volatilize during workup. Some derivatives are prepared by displacement of bda from (benzylideneacetone)iron tricarbonyl (Fe(bda)(CO)3).10.1002/9780470132593.ch11 Inorganic Syntheses 1990 Domingos A. J. P. Howell J. A. S. Johnson B. F. G. Lewis J. Reagents for the Synthesis of η-Diene Complexes of Tricarbonnyliron and Tricarbonylruthenium 28 52–55 9780470132593 Addition of nucleophiles to (pentadienyl) iron tricarbonyl cations gives the neutral diene complex.10.1080/02603599908012010 Pentadienyl Ligands: Their Properties, Potential, and Contributions to Inorganic and Organometallic Chemistry 1999 Ernst Richard D. Comments on Inorganic Chemistry 21 4–6 285–325 Diene complexes can also be produced by dehalogenation of 1,4-dihalobutene derivatives:10.1021/om00054a059 Formation of Iron Carbonyl Complexes of Reactive Polyenes from Dihalides involving the Free Polyene 1991 Kerber Robert C. Ribakove Everett C. Organometallics 10 8 2848–2853 Fe2(CO)9 + C6H4(CH2Br)2 -> FeBr2 + (C6H4(\dCH2)2)Fe(CO)3 + 6 CO The Fe(CO)3 unit serves as a protecting group for the diene, preventing the diene from participating in Diels-Alder reactions and hydrogenation. The diene is usually deprotected with ceric ammonium nitrate.10.1002/ejoc.200900141 Recent Applications of Acyclic (Diene)iron Complexes and (Dienyl)iron Cations in Organic Synthesis 2009 Donaldson William A. Chaudhury Subhabrata European Journal of Organic Chemistry 2009 23 3831–3843 21709767 3121309 Reactions These complexes participate in several reactions of potential value in organic synthesis. The dienes are susceptible to acylation using fairly standard Friedel-Crafts conditions. Once transformed, the diene can be removed with ceric ammonium nitrate as well as trimethylamine N-oxide. Some iron tricarbon complexes of cyclopentadienones catalyze hydrogenation, see Knolker complex. Characterization thumb|Sample of (butadiene)Fe(CO)3, illustrating the color typical of this family of compounds.|220 px|left IR spectra of these complexes show νCO bands near 2040 and 1969 cm−1. At low temperatures, the lower energy band splits, which has been interpreted as evidence for fluxionality on the IR timescale.10.1021/acs.jpca.7b12309 Infrared Dynamics of Iron Carbonyl Diene Complexes 2018 Turner James J. Bühl Michael The Journal of Physical Chemistry A 122 14 3497–3505 29394061 2018JPCA..122.3497T 10023/16989 free References Category:Iron carbonyl complexes