Extending polyoxometalates to palladium

Xu, Feng (2012) Extending polyoxometalates to palladium. PhD thesis, University of Glasgow.

Abstract

This thesis focuses on inorganic polyoxopalladate cluster chemistry, which results from the reactive hydrolysis product of Pd(II). A series of new polyoxopalladates clusters, designated by {Pdn} (n = 4-84, where n is the number of Pd(II) in the cluster), was found in this study.

A supramolecular {Pd17} was first investigated. It was shown that the {Pd17} compound displays a structural variety compared to the parent. Also, a unique interactive
{Pd2} core was found in the centre of the cluster, indicated by an intriguing Pd-Pd short distance of 2.76 A. Furthermore, the host compound with a pristine {Pd15} cage structure was isolated later. Both of the novel structures are well characterized. A possible new type of host-guest chemistry between {Pd15} and {Pd17}, was studied by preliminary P-NMR and UV-Vis measurements.

The facile synthesis of a giant {Pd84} oxo-cluster wheel was revealed. The molecular wheel {Pd84} has an 7-fold symmetry, which is a rare large prime number. Based on the
successfully obtaining another polyoxopalladate cluster, {Pd10}, from a similar synthesis and MS data analysis, a formation mechanism of orderly {Pd84} was proposed. Furthermore, the production organisation of its building block, and driving force to the cyclic shape.

Further investigations focused on synthetic strategies in polyoxopalladates were carried out. A new cage structure of {Pd12} was isolated. The prototype of {Pd12X}, with one
encapsulated transition metal (X = Mn/Co/Ni), has been discussed. In addition, two hybrid polyoxopalladate clusters, {Pd7} and {Pd11}, and two novel Pd-containing sandwich-type polyoxometalates with tetrametallic-cores were revealed.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Subjects: Q Science > QD Chemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Supervisor's Name: Cronin, Prof. Leroy
• Date of Award: 2012
• Embargo Date: 8 February 2015
• Depositing User: MR FENG XU
• Unique ID: glathesis:2012-3178
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 10 Feb 2012
• Last Modified: 10 Dec 2012 14:04
• URI: https://theses.gla.ac.uk/id/eprint/3178