Iron Tetracarbonyl Complexes Research Articles

Substituent Effects on the Chemical Reactivities of Tricarbonyl and Tetracarbonyl Iron Complexes of 7‐Azanorbornadiene Derivatives

AbstractThe intermediates of nitrene‐extrusion reaction were found in the forms of (ANB)Fe(CO)4 or (ANB)Fe(CO)3 during the reaction of 7‐azanorbornadiene derivatives (ANB) with diiron nonacarbonyl. By using extended Hückel molecular orbital (EHMO) calculation, we found that the chemical behavior of these complexes is correlated with the nature of substituents of ANB. The relative reactivity of (ANB)Fe(CO)4 and (ANB)Fe(CO)3 is influenced by the charge distributions on iron and nitrogen. In the crystal structure of (ANB)Fe(CO)4 an angular distortion of Fc‐C=O is observed, which is a result of donor‐acceptor interaction between the lone‐pair of N and the π* orbital of CO.

Darstellung neuer Monofluorphosphine und einiger ihrer Übergangsmetallkomplexe; Einkristall-Röntgenstrukturanalyse eines Platin(II)-Komplexes / Preparation of New Monofluorophosphines and Some of their Transition Metal Complexes; Single Crystal X-Ray Diffraction Study of a Platinum(II) Complex

The reaction of lithiated precursors with PCl2F led to a number of monofluorophosphines, including the known di-tert-butylmonofluorophosphine, 1. Bis(phenylethinyl)monofluorophosphine (2) was accessible only via this route (the classical method of synthesizing 2 by chlorine/fluorine exchange is impossible, because the corresponding chlorophosphine is unknown). Bis(2-methoxyphenyl)fluorophosphine (5) was prepared via the organolithium/PCl2F route. The NMR results for 5 thus prepared were inconsistent with previous reports, implying that the previously reported synthesis of 5 is in error. From 5 a cis-dichloroplatinum(II) complex (6) was synthesized and subjected to a single crystal X-ray structure analysis, confirming the expected planar coordination. From bis(2,3-dimethoxynaphthyl)monofluorophosphine (7) a rhodium(I) (8) and an iron(0)tetracarbonyl complex (9) were prepared. An iron(0)tetracarbonyl complex (11) was synthesized from bis(9-anthryl)monofluorophosphine (10) which was found to be stable to redox disproportionation.

Iron carbonyl-mediated homologous Michael reactions of γ-alkoxy alkenones

Iron tetracarbonyl complexes of γ-benzyloxy-α,β-unsaturated ketones react with several nucleophiles in the presence of Lewis acids to give γ-substitution products. The allyltetracarbonyliron cation intermediates generated allow retention of configuration of the double bond.

Darstellung von 1,3,5-Trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinanen; Einkristall-Röntgenstrukturanalyse eines Platin(II)-Komplexes/Preparation of 1,3,5-Trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinanes; Single Crystal X-Ray Diffraction Study of a Platinum(II)-Complex

A new synthesis for 2-chloro-1,3,5-trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinane (1) is described. Chlorine-fluorine exchange in 1 by means of sodium fluoride in acetonitrile in the presence of catalytic amounts of a crown ether furnished 2-fluoro-1,3,5-trimethyl-4,6-dioxo-1,3,5,2λ3-triazaphosphinane (2). The synthesis of the bromine and iodine analogues, 3 and 4, by metathesis of 1 with the appropriate trimethylsilyl halides, Me3SiBr and Me3SiI, respectively, is also described. The syntheses of an iron(0)tetracarbonyl complex (5) and of a dichloroplatinum( II) complex (6) are reported. A single crystal X-ray diffraction study was conducted on 6. [P21/c, a = 1161.3(3), b = 1423.2(3), c = 1247.7(3) pm, β = 109.42(2)°, R = 0.028], There are deviations from ideal square planar geometry at platinum. The heterocycles display a flattened boat conformation. A Staudinger reaction of 1 with Me3SiN3 led to the formation of a substituted cyclotriphosphazene.

Sulfinyl-controlled formation of diastereoisomerically pure tricarbonyl(oxadiene)iron(0) complexes and a diastereoisomerically pure tetracarbonyl(alkene)iron(0) complex

The sulfonyl and sulfinyl substituted oxadienes [RS(O)nCHCHC(Me)O; R = But, Ph; n= 2,1] form stable tricarbonyliron(0) complexes. The sulfinyl complexes formed are diastereoisomerically pure and the relative stereochemistry of the tricarbonyliron(0) unit and the sulfinyl substituent in the products has been determined by an X-ray crystal structure analysis of [Fe0{ButS(O)CHCHC(Me)O}(CO)3]15a. Phenylsulfonylethene and phenylsulfinylethene form stable tetracarbonyliron(0) complexes. The complex formed from phenylsulfinylethene is diastereoisomerically pure and the relative stereochemistry of the tetracarbonyliron(0) unit and the sulfinyl substituent has been determined by an X-ray crystal structure analysis of [Fe0{PhS(O)CHCH2}(CO)4]18. This reveals evidence for a through-space interaction between the oxygen atom of the sulfinyl substituent and the carbon atom of one of the metal carbonyl ligands. The X-ray crystal structure analysis of [Fe2(µ-CHCH2)(µ-SPh)(CO)6]17, a by-product in the formation of complex 18, is also reported.

Nucleophilic substitution of tetracarbonyliron complexes of γ-acetoxycrotonates: The homologous Michael reaction

Iron tetracarbonyl complexes of γ-acetoxy-α,β-unsaturated esters react with silyl enol ethers in the presence of boron trifluoride-etherate to give substitution in the γ-position. The results are interpreted as being indicative of the intermediacy of a tetracarbonyliron-allyl cation complex which reacts at the terminus remote from the ester function.

ChemInform Abstract: Reactivity of Heterodiene Metal Carbonyl Complexes

Addition of hard nucleophiles to iron tricarbonyl complexes of α,β-unsaturated ketones and iron tetracarbonyl complexes of α,β-unsaturated esters produces γ-ketocarbonyl compounds. Nucleophilic addition to iron tricarbonyl complexes of α,β-unsaturated imines leads either to pyrrole or α,β-unsaturated amine formation

ChemInform Abstract: Synthesis of γ‐Keto Amides (III) via Nucleophilic Attack on Iron Tetracarbonyl Complexes (I) of α,β‐Unsaturated Amides.

ChemInformVolume 20, Issue 45 Heterocyclic Compounds ChemInform Abstract: Synthesis of γ-Keto Amides (III) via Nucleophilic Attack on Iron Tetracarbonyl Complexes (I) of α,β-Unsaturated Amides. A. POUILHES, A. POUILHES Dep. Chem., Univ. Warwick, Coventry CV4 7AL, UKSearch for more papers by this authorS. E. THOMAS, S. E. THOMAS Dep. Chem., Univ. Warwick, Coventry CV4 7AL, UKSearch for more papers by this author A. POUILHES, A. POUILHES Dep. Chem., Univ. Warwick, Coventry CV4 7AL, UKSearch for more papers by this authorS. E. THOMAS, S. E. THOMAS Dep. Chem., Univ. Warwick, Coventry CV4 7AL, UKSearch for more papers by this author First published: November 7, 1989 https://doi.org/10.1002/chin.198945192AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume20, Issue45November 7, 1989 RelatedInformation

Synthesis of γ-ketoamides via nucleophilic attack on iron tetracarbonyl complexes of α,β-unsaturated amides

Organolithium and Grignard reagents react with the readily-formed iron tetracarbonyl complexes of α,β-unsaturated amides to give γ-ketoamides in good yield via acyl transfer from the metal to the β carbon of the α,β-unsaturated amide.

Reactivity of heterodiene metal carbonyl complexes

Addition of hard nucleophiles to iron tricarbonyl complexes of α,β-unsaturated ketones and iron tetracarbonyl complexes of α,β-unsaturated esters produces γ-ketocarbonyl compounds. Nucleophilic addition to iron tricarbonyl complexes of α,β-unsaturated imines leads either to pyrrole or α,β-unsaturated amine formation

Synthesis of alkyl(alkoxycarbonyl)tetracarbonyliron complexes [(Co)4Fe(CH2CO2Me)(CO2R)]: the first evidence of their relevance to the catalytic cycle in the carbonylation of organic halides induced by pentacarbonyliron

Reaction of [(CO)4Fe(CO2R)]–(1)(R = Me or But) with BrCH2CO2Me produces stable complexes [(CO)4Fe(CH2CO2Me)(CO2R)](3) which thermally decompose to yield Fe(CO)5 and malonic esters under a CO atmosphere; these reactions provide the first demonstration of possible key steps in the catalytic cycle of the carbonylation of reactive halides into esters with Fe(CO)5 and an alkoxide anion.

Addition of alkyllithium and Grignard reagents to tetracarbonyliron complexes of α,β-unsaturated esters

Addition of alkyllithium and Grignard reagents to the tetracarbonyliron complexes of methyl acrylate ( 1) and methyl crotonate ( 2) leads to the production of 4-ketoesters via acyl transfer from the metal to the β carbon of the α,β-unsaturated ester.

Low-temperature photochemistry of matrix-isolated iron tetracarbonyl complexes of .alpha.,.beta.-unsaturated esters. Olefinic carbon vs. ester group coordination

Low-temperature photochemistry of matrix-isolated iron tetracarbonyl complexes of .alpha.,.beta.-unsaturated esters. Olefinic carbon vs. ester group coordination

Retention of phosphorus configuration on forming irontetracarbonyl complexes with phosphines in the 9-phosphabicyclo[4.2.1]nonatriene and 7-phosphanorbornene systems

Dimers of phospholes with syn or anti configuration at the bridging phosphorus react with Fe 2(CO) 9 to give complexes, R 3PFe(CO) 4, with complete retention of configuration. Contrary to a report in the literature, isomers of 9-phenylbicyclo[4.2.1]nonatriene also formed complexes with complete retention of configuration.

Structure/reactivity relationships for cationic (phosphenium)iron tetracarbonyl complexes

An X-ray crystal structure of [(Et 2N) 2PFe(CO) 4] +, reveals shortening of the PFe and CO eq bonds and lengthening of the FeC eq bonds, possibly suggesting that the CO lability of cationic (phosphenium)iron tetracarbonyl complexes is due to the strong π-acceptor character of the phosphenium ligand.

A study of .sigma. and .pi. bonding in iron tetracarbonyl complexes

Les energies de liaison des electrons de cœur ont ete mesurees pour une serie de composes du type Fe(CO) 4 L d'apres les spectres XPS. Discussion des resultats

Nicht‐Berry Pseudorotation beim Carbonylgruppenaustausch von Tetracarbonyl(η‐(Z)‐cycloalken)eisen‐Komplexen

Exchange of Carbonyl Group Sites in Tetracarbonyl(η‐(Z)‐cycloalkene)iron Complexes via Non‐Berry PseudorotationThe tetracarbonyliron complexes of cyclobutene, cyclopentene, 4,4‐dimethyl‐cyclopentene, 2,5‐dihydrofurane, cyclohexen, (Z)‐cyclohepten, ‐octene, ‐nonene, and ‐decene were prepared by thermal or photochemical reaction of the corresponding olefins with nonacarbonyldiiron and pentacarbonyliron, respectively. The low‐temperature behaviour of the mostly new complexes which can be stored over a longer period only below 250 K and which exhibit four C,O‐stretching frequencies in the IR. spectra (cf. Table 2), indicative for a trigonal bipyramidal structure with the olefin ligand in an equatorial position, was studied in CCl2F2 by 13C‐NMR. spectroscopy between 200 and 115 K. In this temperature range all complexed olefin ligands with the exception of (Z)‐cyclooctene (cf. [11]) show an averaged Cs‐symmetry on the NMR. time scale. About 115 K the tetracarbonyliron group gives rise to three 13C‐signals in a ratio of 1:1:2 for the complexes of (Z)‐cycloheptene, (Z)‐cyclodecene and 2,5‐dihydrofurane (Cf. Table 3). This is an agreement with the fixed equatorial position of the non‐rotating olefin ligands. The complexes of cyclooctene and cyclononene give only two 13C‐signals in a ratio of 1:1 for the carbonyl groups. The temperature dependence of the signals indicates that in these cases the two axial carbonyl groups exhibit accidentally the same chemical shift. In all cases a complete line shape analysis of the 13C‐signals of the carbonyl groups could only be accomplished by using two exchange constants (cf. Tables 4 and 5 as well as Fig. 2–5 and Fig. 8). The same is true for the cyclobutene complex, but only one exchange constant could be determined (at 120 K: two 13C‐signals in a ratio of 1:3 with the beginning of a further coalescence). The cyclopentene and cyclohexene complexes showed only one 13C‐signal even at 115 K. The observed temperature‐dependent line shapes of the 13C‐signals can be interpreted in terms of a Non‐Berry pseudorotation mechanism involving a three site exchange with each of the two diastereotopic axial carbonyl groups and the two equatorial carbonyl groups (for activation parameters see Table 4). The differences in the activation parameters can be explained on steric grounds by assuming a transition state (cf. Fig. 8) similar to the C3b‐structure of tetracarbonyliron which lies about 27 kJmol−1 above its C2v‐structure (cf. [30]) comparable with the ground state of our complexes with weak dπ(Fe),pπ(Olefin) back bonding. The transition state model implies that the reorganization process involving the axial carbonyl group in exo‐position possesses the higher exchange barrier (cf. Fig. 8).

Reaction of (chlorophosphine)iron tetracarbonyl complexes with aluminum chloride. Iron tetracarbonyl complexes of two-coordinate phosphorus cations

Reaction of (chlorophosphine)iron tetracarbonyl complexes with aluminum chloride. Iron tetracarbonyl complexes of two-coordinate phosphorus cations

Iron carbonyl π-complexes of vinylsilanes, vinyldisilanes and vinylsiloxanes

It is shown that iron carbonyls react with vinylsilanes, CH 2CHSiR 3 (where R is Me, OMe, CHCH 2or Cl) and vinylsiloxanes to give rise to iron tetracarbonyl π-complexes. If two or more vinyl groups are attached to the silicon atom, iron tricarbonyl compounds similar to 1,4-diene complexes are also formed. The reaction of 1,2-divinyltetramethyldisilane with Fe 2(CO) 9 unexpectedly leads also to mono- and bis(iron tetracarbonyl) complexes. IR, 1H and 13C NMR, and mass spectra of the compounds obtained are discussed and some chemical conversions are performed.

ChemInform Abstract: ELECTRONIC STRUCTURE OF ORGANOMETALLIC COMPOUNDS. 7. THE HELIUM (HE I) PHOTOELECTRON SPECTRA OF TETRACARBONYLIRON(0) COMPLEXES WITH CARBENES

Chemischer InformationsdienstVolume 12, Issue 6 Physical Organic Chemistry ChemInform Abstract: ELECTRONIC STRUCTURE OF ORGANOMETALLIC COMPOUNDS. 7. THE HELIUM (HE I) PHOTOELECTRON SPECTRA OF TETRACARBONYLIRON(0) COMPLEXES WITH CARBENES M. C. + BOEHM, M. C. + BOEHMSearch for more papers by this authorJ. DAUB, J. DAUBSearch for more papers by this authorR. GLEITER, R. GLEITERSearch for more papers by this authorP. HOFMANN, P. HOFMANNSearch for more papers by this authorM. F. LAPPERT, M. F. LAPPERTSearch for more papers by this authorK. + OEFELE, K. + OEFELESearch for more papers by this author M. C. + BOEHM, M. C. + BOEHMSearch for more papers by this authorJ. DAUB, J. DAUBSearch for more papers by this authorR. GLEITER, R. GLEITERSearch for more papers by this authorP. HOFMANN, P. HOFMANNSearch for more papers by this authorM. F. LAPPERT, M. F. LAPPERTSearch for more papers by this authorK. + OEFELE, K. + OEFELESearch for more papers by this author First published: February 10, 1981 https://doi.org/10.1002/chin.198106043Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume12, Issue6February 10, 1981 RelatedInformation