Article ID Journal Published Year Pages File Type
1326316 Journal of Organometallic Chemistry 2007 8 Pages PDF
Abstract

The synthesis, characterization and chemistry of novel η3-allyl metal complexes (M = Ir, Rh) are described. The structures of compounds (C5Me4H)Ir(PPh3)Cl2 (1), (C5Me4H)Ir(PPh3)(η3-1-methylallyl)Br (3a), (C5Me4H)Ir(η4-1,3,5-hexatriene) (8), and (C5Me5)Rh(η3-1-ethylallyl)Br (5d) have been determined by X-ray crystallography. Structural comparisons among these complexes are discussed. It is found that the neutral metal allylic complex [Cp∗IrCl(η3-methylallyl)] (5) ionizes in polar solvents to give [Cp∗Ir(η3-methylallyl)]+Cl− (6) and reaches equilibrium (5 ⇌ 6) at room temperature. Addition of tertiary phosphine ligands to neutral complexes such as [Cp∗Ir(η3-methylallyl)Cl], results in the formation of stable ionic phosphine adducts. Factors such as solvent, length of carbon chain, temperature and light are discussed with respect to the formation, stability and structure of the allyl complexes.

Graphical abstractThe synthesis, characterization and chemistry of novel η3-allyl metal complexes (M = Ir, Rh) are described. The neutral metal allylic complex [Cp∗IrCl(η3-methylallyl)] (5) ionizes in polar solvents to give [Cp∗Ir(η3-methylallyl)]+Cl− (6) and reaches equilibrium (5 ⇌ 6) at room temperature. Addition of tertiary phosphine ligands to neutral complexes such as [Cp∗Ir(η3-1-methylallyl)Cl], results in the formation of stable ionic phosphine adduct, [Cp∗Ir(PPh3)(η3-1-methylallyl)]+Cl−.Figure optionsDownload full-size imageDownload as PowerPoint slide

Related Topics
Physical Sciences and Engineering Chemistry Inorganic Chemistry
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