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] 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.
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