Transition metal-stabilised vinylketenes

Hill, Lawrence; Richards, Christopher J.; Thomas, Susan E.

doi:10.1351/pac199062102057

“…Species such as [Fe(CO) 3 (η 4 -PhCHCH−C{Me}O)] have been used as transfer reagents for the Fe(CO) 3 group, and a precise understanding of metal−ligand bonding might enable the design of ligands that will act as better leaving groups . Furthermore, these species have proven to be versatile reagents for the preparation of 1,4-diketones 9 and optically pure ketones, as well as iron(0) vinyl ketene, vinyl ketenimine, 11b, and triene complexes,11b which are also useful synthetic precursors …”

Section: Introductionmentioning

confidence: 99%

A Rationale for the Linear Correlation of Aryl Substituent Effects in Iron(0) Tricarbonyl Complexes Containing α,β-Unsaturated Enone (Chalcone) Ligands

Moulton

¹

,

Duhme‐Klair

²

,

Fairlamb

³

et al. 2007

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A library of iron(0) tricarbonyl complexes containing η4-bound α,β-unsaturated enone ligands [Fe(CO)3(η4-RCHCH−C{Ph}O)] has been prepared to facilitate comprehensive correlation of the electronic withdrawing/donating properties of the substituent, R, with the strength of the metal−ligand interaction. The IR and NMR spectroscopic data proved invaluable in aiding a comprehensive correlation and global understanding of the aryl substituent effects. The frequency of the M−CO bands in the infrared spectra of these species exhibits a linear correlation with the Hammett parameters for the substituents. The coordination shifts in both the 1H and 13C NMR spectra for the ligands exhibit a similar linear relationship. The largest coordination shifts are observed when more electron-withdrawing groups are present, implying that the organic ligand is primarily acting as a π-acid. The structures of six complexes of this type have been determined by single-crystal X-ray diffraction.

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Iron: Organometallic ChemistryBased in part on the article Iron: Organometallic Chemistry by James R. Green which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Paley¹

2005

Encyclopedia of Inorganic Chemistry

2

0

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Studies involving the preparation, reactivity, and properties of the organometallic complexes of iron (compounds possessing a FeC bond) have played a central role in the growth of organometallics as a major subdiscipline with chemistry. From the discovery of ferrocene in the 1950s to the present day, interest and research activity remain high. This entry provides a survey of this large and diverse area of organometallic chemistry, and is arranged by increasing hapticity of the organic ligand of interest that is bound to iron. Included are discussions of the chemistry of iron σ‐alkyl, acyl, alkynyl, and vinyl complexes, iron carbenes, η1‐ and η3‐allyl iron complexes, η2‐alkene and η4‐diene iron complexes, trimethylenemethane and cyclobutadiene complexes of iron, cationic iron pentadienyl, cyclohexadienyl, and arene complexes, and ferrocenes and heteroferrocenes.

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Iron: Organometallic ChemistryBased in part on the article Iron: Organometallic Chemistry by James R. Green which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Paley

¹

2005

Encyclopedia of Inorganic and Bioinorganic Chemistry

1

0

View full text Add to dashboard Cite

Studies involving the preparation, reactivity, and properties of the organometallic complexes of iron (compounds possessing a FeC bond) have played a central role in the growth of organometallics as a major subdiscipline with chemistry. From the discovery of ferrocene in the 1950s to the present day, interest and research activity remain high. This entry provides a survey of this large and diverse area of organometallic chemistry, and is arranged by increasing hapticity of the organic ligand of interest that is bound to iron. Included are discussions of the chemistry of iron σ‐alkyl, acyl, alkynyl, and vinyl complexes, iron carbenes, η1‐ and η3‐allyl iron complexes, η2‐alkene and η4‐diene iron complexes, trimethylenemethane and cyclobutadiene complexes of iron, cationic iron pentadienyl, cyclohexadienyl, and arene complexes, and ferrocenes and heteroferrocenes.

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Transition metal-stabilised vinylketenes

Cited by 8 publications

References 16 publications

A Rationale for the Linear Correlation of Aryl Substituent Effects in Iron(0) Tricarbonyl Complexes Containing α,β-Unsaturated Enone (Chalcone) Ligands

A Rationale for the Linear Correlation of Aryl Substituent Effects in Iron(0) Tricarbonyl Complexes Containing α,β-Unsaturated Enone (Chalcone) Ligands

Iron: Organometallic ChemistryBased in part on the article Iron: Organometallic Chemistry by James R. Green which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Iron: Organometallic ChemistryBased in part on the article Iron: Organometallic Chemistry by James R. Green which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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