Dr Frank Mair (BSc, PhD, MRSC CChem) - research


 

Research interests

Research in my group focuses on generation of new ligands, which form the bedrock of new organometallic and co-ordination chemistry. We tailor these ligands to a variety of functions, but most of these are directed at production of new catalysts for polymerization. This results in the placing of my research group within materials chemistry, a placing also fitted to our parallel interest in self-organised organic materials.

1. Ligand design.

Picture of first anionic complex of this ligand
Picture of first anionic complex of this ligand: Figure 1

Our most significant contribution to the practise of co-ordination chemistry was the first demonstration of the exceptional steric control offered by incorporation of ortho-bulk into the aryl groups of diaryldiketiminate monoanionic ligands. Our 1998 paper1 reporting a potassium complex concluded that "The effectiveness of encapsulation that this ligand topology offers promises rich rewards in wide areas of chemistry". 479 hits for that ligand anion in the CCDC (as at 30/03/07) prove the prescience of this remark.

Then we alkylated the anion to prepare neutral b-diimines. These were originally viewed as competitors to the bulky a-diimines repopularised by Brookhart and others, but the absence of p-acceptor character renders them very weak ligands.2 This led to two parallel developments, both directed at olefin and ethylene polymerization catalysis.

C2-diamidolithium      chemistry
Figure 2, C2-diamidolithium chemistry.
Figure 3. C2 Titanium diamido catalyst giving block-tactic polyhexene
Figure 3. C2 Titanium diamido catalyst giving block-tactic polyhexene

The first path: reduce the ligands, highly diastereoselectively, to make racemic 1,3 diamines,3 lithiate, to make diamido anions,4 (figure 2) then metathesise with TiCl4, to make racemic C2-symmetric diamidotitanium catalysts,5 (Figure 3) desymmetrised and bulkier analogues of McConville?s diamidotitanium catalysts.

The second path: Make super-bulky,strongly p-accepting a-diimines. This is ongoing, to be published. It has parallel applications in polymerization catalysis, and in the promotion of new and unusual reactions, see section 3.

Aside from these amido ligands, derived from b-diketiminates by alkylation followed by reduction, we have developed further elaborations of b-diketiminates, summarised in Scheme 1.

Research Group(s)

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