Photo of Prof Connelly

Professor Neil Connelly

Electron Transfer in Organotransition Metal Chemistry


Our group studies the electron-transfer reactions of transition metal organometallic and co-ordination complexes. This very diverse area involves the use of a wide variety of synthetic, spectroscopic and other methods to study new products and reactions (e.g. IR, NMR, UV-visible, and ESR spectroscopy, simple electrochemistry, and X-ray crystallography in collaboration with Professor A.G. Orpen). Examples from our current work include:

The redox-activation of alkyne and related ligands

The electron transfer reactions of complexes of C2 ligands may lead to simple isomerisation [e.g. of a vinylidene ligand to an alkyne, as in 1 to 2, or to alkyne-containing radicals such as 3 which can be the precursors to new hydrocarbons and heterocycles.

diagram

Redox-active cyanometal complexes

Redox-active cyanide-bridged complexes can show novel electronic and magnetic properties (complex 4 is highly solvatochromic) and provide a better understanding of intramolecular electron-transfer (e.g. in the mixed valence complex 5).

diagram

Metals in novel oxidation states

The oxidation of [M(CO)LTp'] results in the isolation of stable Rh(II) and Ir(II) complexes e.g. 6; unpaired electron density can be selectively controlled in the metal-metal bonds of novel paramagnetic heterobinuclear species such as 7.

diagram

References

Our older research is reviewed in Chem Soc Revs, 1989, 18, 153. (See also Chem Revs, 1996, 96, 877). More recent results can be found in: Chem Commun, 1996, 2289; 1998, 517; 1999, 2403. J Chem Soc, Dalton Trans, 1996, 3977; 1998, 1905, 1913; 1999, 691. Organometallics, 1997, 16, 4369; 1999, 18, 3201.