Skip navigation
Skip navigation

Medium-Nuclearity Mixed-Metal Cluster Chemistry

Fu, Junhong

Description

The thesis is comprised of nine scientific articles and is preceded by an overview that contextualises all of publications. Mixed-metal clusters of group 6 and 9 have been of longstanding interest. The polar metal-metal bonds in these clusters exhibit great potential for substrate activation, and the widely disparate metals could increase cluster reactivity. Our previous studies of group 6 and 9 mixed-metal clusters have been mainly concentrated on...[Show more]

dc.contributor.authorFu, Junhong
dc.date.accessioned2016-11-29T01:38:48Z
dc.date.available2016-11-29T01:38:48Z
dc.identifier.urihttp://hdl.handle.net/1885/110707
dc.description.abstractThe thesis is comprised of nine scientific articles and is preceded by an overview that contextualises all of publications. Mixed-metal clusters of group 6 and 9 have been of longstanding interest. The polar metal-metal bonds in these clusters exhibit great potential for substrate activation, and the widely disparate metals could increase cluster reactivity. Our previous studies of group 6 and 9 mixed-metal clusters have been mainly concentrated on low-nuclearity tetranuclear molybdenum/tungsten-iridium clusters, including the study of their structure, fluxionality, reactivity, electrochemistry, spectroelectrochemistry and optical properties. The thesis project herein mainly focuses on the synthesis of medium-nuclearity clusters of group 6 and 9. The first part of this body of work is concerned with the synthesis of medium-nuclearity molybdenum/tungsten-iridium clusters. Publication 1 details the synthesis of pentanuclear clusters by core expansion of tetranuclear molybdenum/tungsten-iridium clusters with capping reagents tetramethylcyclopentadienyl iridium dicarbonyl and pentamethylcyclopentadienyl iridium dicarbonyl. Publication 2 describes phosphine, isocyanide, and alkyne reactivity at several pentanuclear molybdenum/tungsten-iridium clusters that are reported in Publication 1.Three structurally characterized medium-nuclearity molybdenum-iridium clusters are presented in Publication 3. The second part of the thesis includes the synthesis of medium-nuclearity molybdenum/tungsten-rhodium-iridium clusters by core expansion reactions of tetranuclear molybdenum/tungsten-iridium clusters with capping reagents tetramethylcyclopentadienyl rhodium dicarbonyl and pentamethylcyclopentadienyl rhodium dicarbonyl. Publication 4 delineates a dynamic permutational isomerism in a pentanuclear ditungsten-rhodium-diiridium closo-cluster, together with the proposed mechanism and studies of the chemical and physical properties of the permutational isomers. Publications 5 and 6 detail the syntheses of penta- and hexa-nuclear molybdenum/tungsten-rhodium-iridium clusters by core expansion of tetranuclear molybdenum/tungsten-iridium clusters with the rhodium capping reagents, and phosphine and alkyne chemistry of the pentanuclear clusters. Publication 7 demonstrates the synthesis and structural studies of a hexanuclear trimolybdenum-triiridium cluster and a heptanuclear trimolybdenum-rhodium-triiridium cluster. In addition, Publication 8 describes alkyne chemistry at a phosphine-substituted cluster and explores the impact of phosphine ligation to dimolybdenum-diiridium on optical limiting properties. Finally, Publication 9 reports a four-valence-electron-deficient butterfly tetrairidium cluster and a heptairidium cluster, together with theoretical studies of the tetrairidium cluster.
dc.format.extent1 vol.
dc.format.mimetypeapplication/pdf
dc.language.isoen_AU
dc.publisherCanberra, ACT : The Australian National University
dc.rightsAuthor retains copyright
dc.subjectCrystal structures
dc.subjectMixed-metal
dc.subjectCluster
dc.subjectCarbonyl
dc.subjectCyclopentadienyl
dc.subjectRhodium
dc.subjectIridium
dc.subjectMolybdenum
dc.subjectTungsten
dc.subjectPhosphine
dc.subjectAlkyne
dc.subjectElectrochemistry
dc.titleMedium-Nuclearity Mixed-Metal Cluster Chemistry
dc.typeThesis (PhD)
local.contributor.institutionThe Australian National University
local.contributor.supervisorHumphrey, Mark
local.contributor.supervisorcontactmark.humphrey@anu.edu.au
dcterms.valid2016
local.description.refereedYes
local.type.degreeDoctor of Philosophy (PhD)
dc.date.issued2016-02
local.type.statusAccepted Version
local.contributor.affiliationCollege of Physical & Mathematical Sciences
local.description.embargo20/09/2019
local.request.emailrepository.admin@anu.edu.au
local.request.nameDigital Theses
dcterms.accessRightsRestricted access
dc.provenanceThis thesis has been scanned and made available online through exception 200AB to the Copyright Act.
CollectionsRestricted Theses

Download

File Description SizeFormat Image
Fu, J Thesis 2016.pdf36.54 MBAdobe PDFThumbnail
    Request a copy


Items in Open Research are protected by copyright, with all rights reserved, unless otherwise indicated.

Updated:  22 January 2019/ Responsible Officer:  University Librarian/ Page Contact:  Library Systems & Web Coordinator