15321-51-4Relevant articles and documents
'Salted' iron pentacarbonyl: Molecular isolation in alkali halide solids
Kirkor,David,Michl
, p. 139 - 147 (1990)
The conditions for single-molecule isolation of iron pentacarbonyl by codeposition from vapor phase onto a cold substrate with excess alkali halide vapor have been established. The photochemistry of thus 'salted' Fe(CO)5 has been investigated a
Solid-state nuclear magnetic resonance spectroscopic and quantum chemical investigation of 13C and 17O chemical shift tensors, 17O nuclear quadrupole coupling tensors, and bonding in transition-metal carbonyl complexes and
Salzmann, Renzo,Kaupp, Martin,McMahon, Michael T.,Oldfield, Eric
, p. 4771 - 4783 (1998)
The carbon-13 and oxygen-17 nuclear magnetic resonance spectroscopic shielding behavior, as well as the oxygen-27 nuclear quadrupole coupling constants (NQCC), in the four metal-CO systems Fe(CO)5, Fe2(CO)9, Ni2
Reactions of N-(2-thienylmethylidene)-2-thienylmethylamine derivatives with diiron nonacarbonyl (see abstract)
Tzeng, Yu-Fun,Wu, Chih-Yu,Hwang, Wen-Shu,Hung, Chen-Hsiung
, p. 16 - 26 (2003)
The reaction of N-(2-thienylmethylidene)-2-thienylmethylamine (1) with Fe2(CO)9 under mild conditions in anhydrous benzene yields the iron carbonyl products 2, 3, and 4. Complex 2 is a cyclometallated complex Fe2(CO)6(R-C4 HS-CH2NCH2-C4H3S), in which the organic ligand is (μ-η1:η2-thienyl β-C, α, β-C-C; η1:η 1-(N))-coordinated to the diiron center. Complexes 3 and 4 are novel linear tetrairon complex isomers Fe4(CO)8 (μ-CO)2(R-C4HS-CH- NCH2-C4H3S)2, in which the two organic ligands are (μ-η1-thienyl β-C: η1-N;η2-thienylα, β-C-C:η2-C-N)-coordinated to two diiron centers, respectively. These complexes were well characterized spectrally. The molecular structures of 1a, 2a, 2b, 3a, and 3b have been determined by means of X-ray diffraction. The linear arrangement of the four iron atoms in the 66e clusters 3 and 4 is consistent with the closed valance molecular orbital (CVMO) theory. Complexes 3 and 4 may be viewed as consisting of a central Fe2(CO)2(μ-CO) 2 core to which two η5-azaferracyclopentadieny fragments are coordinated; hence 3 and 4 are isolobally-related analogues of [CpFe(CO)(μ-CO)]2. Thermal reaction of 3 or 4 in hexane, benzene, or acetonitrile leads to the decomposition of the complex. No interconversion between isomers 3 and 4 has been observed.
Observation of Photochemical Intermediates in the Low-Temperature Photolysis of Silica-Adsorbed Fe(CO)5
Trusheim, Mark R.,Jackson, Robert L.
, p. 1910 - 1916 (1983)
The photochemistry of silica-adsorbed Fe(CO)5 has been examined at reduced temperatures with a frequency-tripled Nd:YAG laser (355 nm) as the light source.The only significant photoproduct observed by IR spectroscopy upon photolysis at temperatures between 200 and 300 K is Fe3(CO)12; no Fe(CO)9 is detected.Photolysis at 100 to 150 K also yields Fe3(CO)12, but another major product is formed as well.On the basis of IR spectra obtained in the carbonyl stretching region, this product is assigned as Fe(CO)4(SiO2), which denotes the species formed upon addition of a silica surface hydroxyl group or siloxane bridging oxo group to the primary photoproduct, Fe(CO)4.This species is a key intermediate in the photoinitiated conversion of Fe(CO)5 to Fe3(CO)12 in tis system.Photolysis experiments were also carried out at temperatures below 100 K, but here Fe(CO)5 apparently aggregates on the silica surface, complicating interpretation of the photochemistry.
Syntheses and structures of iron carbonyl complexes derived from N-(5-methyl-2-thienylmethylidene)-2-thiolethylamine and N-(6-methyl-2-pyridylmethylidene)-2-thiolethylamine
Wu, Chih-Yu,Chen, Lih-Hau,Hwang, Wen-Shu,Chen, Huang-Shiuh,Hung, Chen-Hsiung
, p. 2192 - 2200 (2004)
The reaction of N-(5-methyl-2-thienylmethylidene)-2-thiolethylamine (1) with Fe2(CO)9 in refluxing acetonitrile yielded di-(μ3-thia)nonacarbonyltriiron (2), μ-[N-(5-methyl-2-thienylmethyl)-η1:η1 (N);η
1,3-Dipolar cycloaddition to the Fe-S=C fragment 20. Preparation and properties of carbonyliron complexes of di-thiooxamide. Reactivity of the mononuclear (di-thiooxamide)Fe(CO)3 towards dimethyl acetylenedicarboxylate
Siebenlist, Ron,Frühauf, Hans-Werner,Kooijman, Huub,Veldman, Nora,Spek, Anthony L,Goubitz, Kees,Fraanje, Jan
, p. 66 - 89 (2002)
Reaction of Fe2(CO)9 at room temperature in THF with the di-thiooxamides (L), S=C{N(R,R′)}-C{(R,R′)N}=S [R=Me, R′-R′=(CH2)2 (a); R=H, R′=iPr (b); R=H, R′=iPr (c), R=H, R′=benzyl (d); R=H, R′=H (e)], results for ligands a-d initially in the formation of the mononuclear σ-S, σ-S′ chelate complexes Fe(CO)3(L) (7a-d), which could be isolated in case of 7a and 7d. Under the reaction conditions, complexes 7a-d react further with [Fe(CO)4] fragments to give three types of Fe2(CO)6(L) complexes (8a-d) in high yields, depending on the di-thiooxamide ligand used together with traces of the known complex S2Fe3(CO)9 (14). The molecular structures of these complexes have been established by the single crystal X-ray diffraction determinations of 8a, 8b and 8d. In the reaction with ligand e the corresponding complex 7e was not detected and the well-known complexes 14 and S2Fe3(CO)9 (15) were isolated in low yield. In situ prepared 7a reacts in a slow reaction with 1 equiv. of dimethyl acetylene dicarboxylate in a 1,3-dipolar cycloaddition reaction to give the stable initial ferra [2.2.1] bicyclic complex 10a in 60% yield. In complex 10a an additional Fe(CO)4 fragment is coordinated to the sulfido sulfur atom of the cycloadded Fe-S=C fragment. When a toluene solution of 10a is heated to 50 °C it loses two terminal CO ligands to give the binuclear Fe-Fe bonded complex 11a in almost quantitative yield. The molecular structures of 10a and 11a have been confirmed by single crystal X-ray diffraction. Reaction of 7d at room temperature with 2 equiv. of dimethyl acetylene dicarboxylate results in the mononuclear complex 12d in 5% yield. The molecular structure of 12b has been established by single crystal X-ray diffraction and comprises a tetra dentate ligand with two ferra-sulpha cyclobutene, and a ferra-disulpha cyclopentene moiety. When the reaction is performed at 60 °C a low yield of 2,3,4,5-thiophene tetramethyl tertracarboxylate is obtained besides complex 12d.
Low-valent α-diimine iron complexes for catalytic olefin hydrogenation
Bart, Suzanne C.,Hawrelak, Eric J.,Lobkovsky, Emil,Chirik, Paul J.
, p. 5518 - 5527 (2008/10/09)
A family of low-valent α-diimine iron complexes has been synthesized and their utility in catalytic olefin hydrogenation reactions evaluated. Reduction of the ferrous dichloride complex [ArN=C(Me)C(Me)=NAr]FeCl2 (Ar = 2,6-(CHMe2)2-C6H3) with sodium amalgam in benzene or toluene furnished the iron arene complexes, [ArN=C(Me)C(Me)=NAr]Fe(η6-C6H5R) (R = H, Me). The solid-state structure of the toluene adduct revealed a contracted carbon-carbon backbone, short iron-imine bonds, and elongated imine nitrogen-carbon distances, suggesting significant reduction of the α-diimine ligand. The analogous reduction in alkane solvents afforded the bis(α-diimine) complex [ArN=C(Me)C(Me)=NAr]2Fe, which has also been crystallographically characterized. The arene complexes and the bis(a-diimine) complexes are inactive for catalytic olefin hydrogenation. Performing the reduction in the presence of internal alkynes such as diphenylacetylene and bis(trimethylsilyl)acetylene furnished the alkyne adducts [ArN=C(Me)C(Me)=NAr]Fe(η2-RC=CR) (R = Ph, SiMe3 ). Analogous olefin complexes with 1,5-cyclooctadiene and cycloctene have also been isolated using similar reduction procedures. The olefin adducts provide more active precatalysts than the alkyne compounds for the hydrogenation of 1-hexene. In each case, formation of rfarene adducts serves as a major catalyst deactivation pathway.
