This project set out to provide high resolution NMR support for a range of research in synthetic chemistry, NMR method development, and mechanistic studies. The equipment funds of £240k were combined with the specified University contribution of £35k and a further £59.7k. This enabled both the purchase of a Varian INOVA 400 multinuclear spectrometer and the provision of INOVA consoles for two existing 300 MHz magnets, giving a total of 3 spectrometers. The autosampler robot was fitted to one of the 300 MHz instruments to provide a rapid open-access service for 1D and 2D experiments; both this and the two remaining instruments have operated 24 hours a day for the period of the grant with only minor interruptions for repairs. The three instruments have underpinned a wide range of science, summarised below, resulting in over 160 publications and £3.5M of successful grant applications.

Medium field NMR has proved essential in underpinning research into synthetic and mechanistic organic and polymer chemistry. Areas of interest during the tenure of this grant include:
* aspects of organotin chemistry, specifically for remote asymmetric induction, and other organometallic chemistry, e.g. the Dötz reaction;
* the total synthesis of complex natural products, e.g. the completion of a synthesis of milbemycin G and several marine alkaloids;
* studies of atropisomerism with reference to stereochemical control and the elucidation of the stereoselectivity of fundamental organometallic processes;
* studies of methods for oxidation and reduction, the directed hydroxylation of alkenes and the Birch reduction of heterocycles being of particular interest;
* studies into the synthesis and chemistry of molybdenum cofactors;
* the further development of 'living' polymerisation;
* physical organic studies of fragmentation processes and substituted crown ethers as enzyme mimics;
* the development of polymer-supported catalysts for asymmetric synthesis that can achieve enantiomeric excesses of 98%;
* the synthesis of libraries of macrocyclic crown-ester analogues;
* the conversion of condensation polymers into families of cyclic oligomers; and
* the synthesis of novel phthalocyanine-centred dendrimers and phthalocyanine sheet polymers.

The period of this grant has been a productive one for NMR research, with major advances made in automated shimming methods, diffusion-ordered spectroscopy (DOSY) and techniques for overcoming some of the inherent limitations of NMR instrumentation. Automated methods for 1D and 3D shimming of high resolution spectrometers have been developed that are fast, robust and accurate. Such methods are already being implemented in the latest commercial spectrometers. High resolution diffusion-ordered spectroscopy (HRDOSY) NMR techniques allow the NMR spectra of mixtures to be resolved into component subspectra from species with different diffusion coefficients. A series of improved pulse sequences for HRDOSY has been published, including a 3D DOSY-HMQC experiment which offers the highest resolution yet achieved by any DOSY method. Software developed in Manchester for the processing of DOSY data and construction of DOSY spectra is in use in a range of academic and industrial laboratories.

Multinuclear and 2D NMR methods have proved particularly valuable in synthetic inorganic chemistry. The coordination chemistry of Mo and W dithiolene complexes, which supports studies to understand the role of these metals in enzymes has been extended; in a complementary study, the total synthesis of the organic component of the cofactor in these enzymes is nearly complete. The new area of coordination chemistry identified in the natural product Amavadin has been extended throughout Groups 4 and 5 of the periodic table. The organometallic chemistry of cyclohepta trienyl and -dienyl compounds and the coordination chemistry of cobaloximes and poly(imidazole) ligands have been extended. A new programme concerning solution speciation of metal-organic actinide complexes has begun.

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Most recent revision 4th October 2001