Research project: Reid: Thioether ligand chemistry
Currently Active:
Yes
Early work involved detailed electrochemical and structural studies of aza and thioether macrocyclic complexes, including stabilisation of very rare examples of mononuclear Pd(I), Pd(III), Ag(II) and Rh(II) centres.
Project Overview
We are particularly interested in investigating the coordination chemistry of soft thioether ligands with hard, oxophilic early transition metal centres, including Cr(III), V(III) and (IV), M(IV) (M = Ti, Zr and Hf), including the unusual 7-coordinate [ZrCl
4
([9]aneS
3
)], and very recently, structural authentication of the first Mo(VI) thioether species, cis-[MoO
2
X
2
{RSCH
2
CH
2
SR}] (R = Me or Et) and the very unusual dimeric [Mo
2
O
4
Cl
4
{o-C
6
H
4
(CH
2
SMe)
2
}
2
] and characterisation of the first series of W(VI) complexes with thioether ligands, including [WO
2
X
2
{iPrS(CH
2
)
2
S
i
Pr}]. The recent Mo(VI) and W(VI) chemistry is in collaboration with Dr Ratnani, MDS University, Ajmer, India. We have also demonstrated an unexpected preference for S over O coordination in mixed thia-oxa crowns towards hard V(III) and Cr(III) species.
We are developing a unique freeze-quench XAFS system to allow investigation of the mechanism(s) of selective ethene oligomerisation catalysed by Cr complexes with multidentate S- and N-based complexes via XAFS spectroscopy and XANES studies (with Prof. J. Evans and Dr M. Tromp). New ditopic S-based receptors for specific combinations of hard and soft transition metals are being developed as precursors to supported bimetallic sulfide particles.
Synthesis and Molecular Structures of Six-, Seven- and Eight-Coordinate Zr(IV) and Hf(IV) Complexes Involving Thioether and Selenoether Ligands.
R. Hart, W. Levason, B. Patel and G. Reid, J. Chem. Soc., Dalton Trans., 2002, 3153.
Synthesis, spectroscopic and structural properties of hexavalent molybdenum complexes with thio- and seleno-ether ligands.
M. D. Brown, M. B. Hursthouse, W. Levason, R. Ratnani, G. Reid, Dalton Trans., 2004, 2487-2491.
Studies on Chromium(III) and Vanadium(III) Complexes With Crown Ether and Crown Thioether Coordination - Synthesis, Properties and Structural Systematics.
C. D. Beard, L. Carr, M. F. Davis, J. Evans, W. Levason, L. D. Norman, G. Reid and M. Webster, Eur. J. Inorg. Chem., 2006, 4399-4406.
Vanadium(IV) and oxidovanadium(IV) and (V) complexes with soft thioether coordination - synthesis, spectroscopic and structural studies
A. L. Hector, W. Levason, A. J. Middleton, G. Reid and M. Webster, Eur. J. Inorg. Chem., 2007, 4391-4398.
Probing the effects of ligand structure on activity and selectivity of new Cr(III) complexes for ethylene oligomerization and polymerization
J. O. Moulin, J. Evans, D. S. McGuinness, G. Reid, A. M. Rucklidge, R. P. Tooze and M. Tromp, Dalton Trans., 2008, 1177-1185.