Name: Ajay Venugopal
Diploma / M.Sc degree: University of Pune, India
(May 2004)
Title: Syntheses, Structure and Reactivity of Hydroxylamine Complexes of Yttrium, Lanthanum and f-Block Elements


Homepage: www.uni-muenster.de/Chemie.ac/mitzel/welcome.html

Abstract of Research Project

One current trend in the field of Y, La and the f-elements chemistry is the search for non-cyclopentadienyl complexes exhibiting low coordination numbers and catalytic activity. The chemistry of these compounds is often governed more by electrostatic and steric factors than by orbital interactions.

Hydroxylamine ligands can be bound to the metal centres of organometallic fragments and bear an additional donor function in close proximity to the metal centre. This opens up the possibility for the formation of three-membered MON rings. The latter coordination mode is thought to lead to a saturation of the coordination sphere using very small ligands, which is normally difficult to achieve in the case of the chosen metals. Two synthetic routes will be employed for the syntheses: (i) amine elimination pathway using Ln{N(SiMe₃)₂}₃ and (ii) using Ln{CH(SiMe₃)₂}₃ as precursor complexes (Ln = Y, La, f-block elements).

The study of the structural chemistry of hydroxylamine complexes of Ln (III) atoms will provide fundamental information about their geometry, aggregation and fluxional behaviour in solution. The project will also involve investigation on their implications in catalysis owing to the Lewis-acidity of the complexes, and of molecular cations derived from those.


Publications

A. Venugopal, I. Kamps, D. Bojer, R. J. F. Berger, A. Mix, A. Willner, B. Neumann, H.-G. Stammler, N. W. Mitzel
Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state
Dalton Trans. 29 (2009), 5755-5765.

A. Venugopal, T. Pape, A. Willner, N. W. Mitzel
Bis(hydroxylaminato)-mono(pentamethylcyclopentadienyl) rare-earth metal complexes
Dalton Trans. 29 (2009), 5715-5719.


Ajay Venugopal
eMail: Ajay Venugopal