Prof Alice C. Sullivan

Professor in Inorganic Chemistry
BA Mod.Chem (1979 Trinity College Dublin)
PhD (1982) with Prof. DJ Cardin (TCD)

School of Biological & Chemical Sciences
Queen Mary, University of London
Walter Besant Building, Mile End Road
London
E1 4NS
Tel: +44 (0) 20 7882 3274
Fax: +44 (0) 20 7882 7427
email: A.C.Sullivan@qmul.ac.uk

Research Interests

Design and synthesis of novel porous organosilicon materials from molecular precursors with in-built features to influence subsequent applications in catalysis and separation processes. The comparative environmental benefits of solid phase catalytic approaches are amply demonstrated particularly from zeolite successes. However the limitations of zeolites and other existing solid phase materials for liquid phase transformations are well documented. In this context we recently developed novel aminopropyl modified polysilsesquioxanes and demonstrated that these mesoporous materials are excellent and in some cases superior solid base catalysts for Knoevenagel condensation processes compared to related silica analogues of similar pore size. Green Chemistry 2002, 4, 239-244. We have recently developed new families of mesoporous silicas and polysilsesquioxanes with covalently attached phosphonic acid groups. J. Mat. Chem., 2000, 10, 2758-2764; Chem. Commun., 2001, 67-68. The phosphonic acid function is attractive because it offers potential activity over a broad pK range and excellent binding sites for metal cations. The new solid acids range from single component phosphonic acid modified T-frameworks, two-component phosphonic acid modified Q frameworks,and three component phosphonic acid modified T/Q frameworks. A particular aim is to provide new functional solid reagents for wide-ranging applications as solid protic and Lewis-acid

catalysts, as ion exchange and porous support media and as materials for chromatographic separation. The materials may be studied using solid state NMR spectroscopy (for local chemical structure) and porosimetry and microscopy (for texture). In recent work we have demonstrated that metal phosphonate derivatives of the phosphonic acid modified materials are readily obtained . The materials are excellent BrØnsted and Lewis acid catalysts in a wide range of organic chemistries. J. Mater. Chem., 2002, 12, 3605 - 3609. Tetrahedron Letters, 2003, 44(4), 769-771; .Selective oxidation activity for a range of fine chemical substrates looks very promising Tetrahedron Letters, 2003, 4283-4286 We have identified a commercially attractive family within this group of materials (A.C. Sullivan and J.R.H.Wilson, WO/02055587) and recently set up the university spin-out PhosphonicS Ltd to exploit this solid phase platform.

• Other key interests include investigation of new families of coordination compounds with elaboration of solid state and solution structural chemistry and reactivity in terms of likely applications in catalysis, for materials synthesis, or as reagents in organic chemistry or in sensing applications. We have significantly developed the co-ordination chemistry of a,w-siloxanediolate and silanediolate ligands These compounds are of interest as precatalysts for olefin polymerisation, as precursors for metal oxide/silica materials (own results) in connection with possible intermediates in anionic ring opening polymersiation of cyclic siloxanes (our work and the topic is reviewed in Coord. Chem. Rev., 1999, Vol.189, pp.19-57).
• We are interested in the development of bis-imido and oxo-imido complexes as catalysts for oxidation.(J. Chem.Soc. Dalton Trans 2000, 1357-1361;) The cis-orientation of the electron-donating oxo and imido groups in these compounds turned out to be dominant even in the presence of tetradentate Schiff bases with a preference for planar arrangements. Very low oxidation potentials are observed which turned out to be associated with HOMO occupation of a delocalised orbital on the two imido groups. J. Chem. Soc., Dalton Trans., 2003, 3591 Some of these oxo-imido catalysts are highly selectivie in catalytic oxidation chemistry. J. Chem. Soc., Dalton Trans., 2003, submitted.
• We are currently trialling a range of novel molecular phosphonate chemistry which will form a major new line of investigation for us over the next few years (New Journal of Chemistry., 2002, 26, 433-439 plus several manuscripts in preparation)

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