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Metal-Ligand Bonds

Metal-Ligand Bonds

The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...

Properties of Organometallic Compounds

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Complexation Equilibria: The Chelate Effect

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

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Complexation Equilibria: Factors Influencing Stability of Complexes

Complexation Equilibria: Factors Influencing Stability of Complexes

In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...

Oxidative Cleavage of Alkenes: Ozonolysis

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Preparation of SNS Cobalt(II) Pincer Model Complexes of Liver Alcohol Dehydrogenase

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Transition metal-alkane σ-complexes with oxygen donor co-ligands.

Rowan D Young¹, Anthony F Hill, Warwick Hillier

¹Institute of Advanced Studies, Australian National University, Canberra, ACT, Australia.

Journal of the American Chemical Society

|July 19, 2011

Summary

Researchers discovered new long-lived alkane sigma-complexes using spectroscopy and computation. These complexes, featuring oxygen-rich coordination spheres, may model intermediates in hydrocarbon transformations.

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Area of Science:

Organometallic Chemistry
Inorganic Chemistry
Computational Chemistry

Background:

Alkane sigma-complexes are crucial intermediates in catalytic hydrocarbon functionalization.
Understanding the structure and reactivity of these complexes is key to developing new catalytic processes.

Purpose of the Study:

To synthesize and characterize a novel family of long-lived alkane sigma-complexes.
To investigate the electronic and structural properties of these complexes using spectroscopic and computational methods.
To assess their potential as models for intermediates in metal oxide-mediated hydrocarbon transformations.

Main Methods:

Synthesis of (L(OEt))Re(CO)(2)(alkane) complexes, where L(OEt) = cyclopentadienyltris(diethylphosphito)cobaltate(III) and alkane = cyclopentane, cyclohexane, or pentane.
Characterization using Infrared (IR) and Nuclear Magnetic Resonance (NMR) spectroscopies.
Computational analysis employing Density Functional Theory (DFT) methods.

Main Results:

Observation of a new family of long-lived alkane sigma-complexes.
Detailed structural and electronic characterization through combined experimental and computational data.
Identification of oxygen-rich coordination spheres in the studied complexes.

Conclusions:

The newly synthesized alkane sigma-complexes are stable and well-characterized.
Their unique oxygen-rich coordination environment suggests relevance as models for catalytic intermediates.
These findings advance the understanding of metal-mediated hydrocarbon transformations.