(Dihydropyridine)iron tricarbonyl complexes

(N-Carboalkoxy-1,2-dihydropyridine)iron tricarbonyl complexes have been isolated by treatment of either N-carboalkoxy-1,2 or -1,4-dihydropyridines with diiron ennecarbonyl. The organic ligand was liberated from these complexes by use of trimethylamine oxide.     

Diastereoselective spiroketalization: stereocontrol using an iron(0) tricarbonyl diene complex

It has been demonstrated that an element of planar chirality can influence the formation of an adjacent spiroketal stereocenter. Appropriately functionalized enantiomerically pure 1- and 2-sulfinyl 1,3-dien-5-ones and their corresponding iron(0) tricarbonyl complexes (7, 17) have been prepared, and the derived spiroketals (8, 18) are made in good to excellent diastereoselectivity. A preliminary exploration of the combined effects of planar and central chirality upon the diastereoselectivity revealed matched and mismatched combinations (14).     

Synthesis and structural characterization of tricarbonyl 1-azahexa-1,3,5-triene iron(0) complexes

Transition Metal Chemistry -     

Synthetic studies with iron carbonyl complexes. Versatile synthesis of olefinic side-chains to a tricarbonyl(cyclohexadiene)iron(0) ring

Tricarbonyl(cyclohexadiene)iron(0) complexes bearing olefinic side-chains at the 2- or the 5-position have been prepared by a versatile route. Terminal olefins are isomerised to internal isomers. The presence of a methoxy substituent at the 2-position prevents isomerisation of the coordinated diene into conjugation with the olefin, so locking the side-chain at the 5-exo-position.     

The vibrational spectrum of (trimethylenemethane)iron tricarbonyl

A vibrational assignment for the trimethylenemethane molecule, in [C(CH₂)₃]Fe(CO)₃, has been proposed for the first time. CC₃ stretches were found at 1348 (E) and 918 cm⁻¹ (A₁), with skeletal deformations at 802 cm⁻¹ (A₁, out-of-plane), and 471 cm⁻¹ (E, in plane). The Fe(CO)₃ vibrations were closely similar to those in analogous complexes.     

Synthetic studies relating to acetylergosterol-(tricarbonyl)iron

Acetylergosterol(tricarbonyl)iron has been prepared in good yield using benzylideneacetone(tricarbonyl)iron. The steroidal complex may be hydroborated or subject to osmolysis, to yield potential vitamin D precursors.     

New tricarbonyl(amido-substituted-1,3-diene)iron complexes

X-substituded benzamides (X = H; 2-OH; 4-MeO; 3-MeO; 3,5-(MeO)₂; 4-Cl and 2,4-Cl₂) have been shown to add reversibly to the dienyl rings of the organometallic compounds [(dienyl)Fe(CO)₃]BF₄ (dienyl = C₆H₇, 2-MeOC₆H₆ or C₇H₉) to give the corresponding cationic tricarbonyl(substituted-diene)iron complexes.     

Stereochemical leakage mechanisms for tricarbonyl(dienyl)iron cations

ψ-Endo to ψ-exo leakage during solvolysis of a ψ-endo-dienol—Fe(CO)₃ dinitrobenzoate ester does not proceed via a syn, syn-cis-dienyl—Fe(CO)₃ cation. The most probable leakage mechanism involves non-stereospecific ionization of the dinitrobenzoate ester. syn,syn-cis-Dienyl—Fe(CO)₃ cations are formed from ψ-exo-dienol—Fe(CO)₃ complex during chromatography on grade I neutral alumina.     

Reaction of tricarbonyl(dienal)iron complexes with B-allyldiisopinocampheylborane

Addition of allyldiisopinocampheylborane to racemic (dienal)iron complexes, followed by oxidation, affords diastereomeric (1,4,6-trien-3-ol)iron complexes with moderate to low enantioselectivity. The high enantioselectivity typically observed for this allylborane reagent is attenuated by steric interaction between the Fe(CO)₃ group and the chiral isopinocampheyl groups. Further diminution of the enantioselectivity is observed for dienal complexes in which one rotomer predominates.     

Enantiopure eta4-(1-sulfinyldiene)iron(0) tricarbonyl complexes as templates for carbocycle construction via ring-closing metathesis

[reaction: see text] Enantiomerically pure 1-(1Z,3E)-sulfinyl iron(0) dienols have been elaborated to bis-olefins capable of undergoing ring-closing metathesis chemistry. Using Grubbs' ruthenium carbene catalyst, a six-membered carbocycle (with one chiral center) and seven-, eight-, and nine-membered carbocycles (with two chiral centers) have been prepared. Novel transformations include the LiClO4-promoted allylation of an alkylidene malonate and a reductive sulfur-carbon bond cleavage to convert a vinyl sulfoxide into an alkene with SmI2.     

Linkage isomerism in 5-exo thiocyanate and isothiocyanate substituted tricarbonyl(η-cyclohexa-1,3-diene)iron and tricarbonyl(η-cyclohepta-1,3-diene)iron

Nucleophilic addition to the tricarbonyl(η-cyclohexadienyl)iron cation and the tricarbonyl(η-cycloheptadienyl)iron cation by the thiocyanate ion forms initially the 5-exo-isothiocyanate (NCS) isomers, C₆H₇NCSFe(CO)₃ and C₇H₉NCSFe(CO)₃, both of which isomerise to the corresponding 5-exo thiocyanate isomers C₆H₇SCNFe(CO)₃ and C₇H₉SCNFe(CO)₃ on exposure to air.     

The electrophilic acetylation of tricarbonyl(cyclohexa-1,3-diene)iron

Friedel—Crafts acetylation of the title compound yielded as the major reaction product a $\text{4}\text{1}$ mixture of the 5-exo- and 5-endo-acetyl complexes. The major component of the mixture was shown to be the exo isomer by comparison with an authentic sample, synthesised stereospecifically.     

Organometallic polymers containing tricarbonyl(η4-diene)-ruthenium(0) and -iron(0) as pendant groups

Vinyl ethers containing tricarbonyl(14-η⁴-1,3-pentadiene)-ruthenium(0) and -iron(0) species were prepared utilizing selective dienylation with penta-dienylpotassium and were polymerized with cationic initiators to give high molecular weight polymers. The diene-metal moieties were converted into tricarbonyl(13-η³-allyl)metal species by protonation with dry HCl. Tricarbonyl(3-allyl-14-η⁴-1,3-pentadiene)iron(0) also undergoes cationic polymerization but the presence of its isomer, tricarbonyl(3-propenyl-14-η⁴-1,3-pentadiene)iron(0) inhibits the polymerization.     

Mass spectrometric study of tricarbonyl (eta(6)-phenyl methanols) of chromium(0)

A mass spectrometric study of several tricarbonyl (eta(6)-phenyl methanols) of chromium(0) was performed. Electron ionization (EI), chemical ionization (CI) and fast atom bombardment (FAB) mass spectra were acquired for each molecule, and compared in order to establish a general fragmentation pattern. The suggested pathways were investigated and confirmed by means of constant b/e linked scans and high resolution data. In addition a Hammett-McLafferty correlation for some peaks derived from the molecular ions was accomplished.