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The University of Southampton

s-Block and Transition Metal Complexes - Structure and Small Molecule Reactivity Investigations Seminar

6 May 2015
Building 27, Room 2003 Chemistry University of Southampton Southampton SO17 1BJ

For more information regarding this seminar, please email Geoff Hyett at .

Event details

Deborah Kays presents a seminar as part of the FIMS research groups seminar series.

During this talk, two areas of research from our group will be discussed – the stabilisation and structures of highly reactive alkaline earth compounds and the structure and reactivity of low-coordinate transition metal complexes using sterically demanding m-terphenyl ligands.

The use of sterically demanding carbazol-9-yl ligands facilitates the stabilisation of highly reactive s-block complexes;1 these bulky anions effectively shield the metal cations, thereby minimising aggregation and coordination by extraneous Lewis bases. Structural investigations of Hauser bases 1,3,6,8-tBu4carbMgI(THF)2 (1) and 1,8-Mes2-3,6-tBu2carbMgI(THF) (2; Mes = 2,4,6-Me3C6H2) highlight significant differences in the coordination motifs depending on the nature of the carbazolyls: 1,8-di(tert-butyl) substituted ligands afford π-type compounds in which the carbazolyl ligand acts as a multihapto donor, while 1,8-diaryl substituted ligands afford σ-type complexes.2

Bulky m-terphenyl ligands such as 2,6-Mes2C6H3 ¯ facilitate the isolation of rare two-coordinate transition metal aryl complexes; (2,6-Mes2C6H3)2M (M = Mn, Fe, Co).3 The use of the 2,6-Naph2C6H3‾(Naph = 1-C10H7) ligands generally affords three-coordinate complexes, where, as a result of limited conformational flexibility multiple conformations are available;4 this is supported by calculations and spectroscopic measurements.

click on image to enlarge

Small molecule reactivity investigations reveal that small changes in the m-terphenyl frameworks and metals used lead to significant modification of chemical reactivity. Reactions with dry carbon monoxide have yielded products including a highly encumbered benzophenone and a terphenyl-substituted keto-fluorenone (3).5 These unusual products are formed through M−C bond breaking and C–C bond forming reactions, and can introduce new stereocentres in the products.



1. R. S. Moorhouse, G. J. Moxey, F. Ortu, T. J. Reade, W. Lewis, A. J. Blake, D. L. Kays, Inorg. Chem. 2013, 52, 2678–2683.

2. F. Ortu, G. J. Moxey; A. J. Blake; W. Lewis, D. L. Kays, Chem. Eur. J. 2015, in press. DOI: 10.1002/chem.201406490.

3. D. L. Kays (née Coombs), A. R. Cowley, Chem. Commun. 2007, 1053–1055.

4. B. M. Gridley, G. J. Moxey, W. Lewis, A. J. Blake, D. L. Kays, Chem. Eur. J. 2013, 19, 11446–11453.

5. B. M. Gridley, A. J. Blake, A. L. Davis, W. Lewis G. J. Moxey and D. L. Kays, Chem. Commun. 2012, 48, 8910–8912.


Speaker information

Dr Deborah Kays, University of Nottingham. School of Chemistry

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