The [M(NHC)] (M=Pd, Pt) fragment in the synthesis of heteronuclear clusters

While heteronuclear clusters having phosphine ligands are well-known, those containing nitrogen heterocyclic carbenes (NHCs) seem less explored. This describes work on the synthesis and characterization of new heteronuclear clusters of the heavier groups 8 (Ru and Os) and 10 (Pd and Pt) metals conta...

Full description

Saved in:
Bibliographic Details
Main Author: Liu, Yu
Other Authors: Leong Weng Kee
Format: Theses and Dissertations
Language:English
Published: 2014
Subjects:
Online Access:https://hdl.handle.net/10356/61775
Tags: Add Tag
No Tags, Be the first to tag this record!
Institution: Nanyang Technological University
Language: English
id sg-ntu-dr.10356-61775
record_format dspace
spelling sg-ntu-dr.10356-617752023-02-28T23:36:39Z The [M(NHC)] (M=Pd, Pt) fragment in the synthesis of heteronuclear clusters Liu, Yu Leong Weng Kee School of Physical and Mathematical Sciences DRNTU::Science While heteronuclear clusters having phosphine ligands are well-known, those containing nitrogen heterocyclic carbenes (NHCs) seem less explored. This describes work on the synthesis and characterization of new heteronuclear clusters of the heavier groups 8 (Ru and Os) and 10 (Pd and Pt) metals containing nitrogen heterocyclic carbenes (NHC). The reactivity of the [M(NHC)] (where M = Pd or Pt) synthon with various group 8 metal carbonyl clusters afforded a new synthetic methodology for such heterometallic clusters. A number of these clusters have been prepared and fully characterized, and their stability and reactivity investigated. A reasonable mechanism for their formation, supported by computational studies, has been proposed. In the course of this study, it was found that the reaction of free NHCs with the osmium carbonyl cluster Os3(CO)12 afforded a stable, zwitterionic, acyl metalate cluster. This cluster has been isolated and fully characterized, including by an X-ray crystallographic study, and it has been shown to lead to an NHC-substituted cluster. This represents the first direct structural evidence that nucleophilic substitution in carbonyl complexes involves initial nucleophilic attack at a carbonyl ligand. DOCTOR OF PHILOSOPHY (SPMS) 2014-10-08T01:35:40Z 2014-10-08T01:35:40Z 2014 2014 Thesis Liu, Y. (2014). The [M(NHC)] (M=Pd, Pt) fragment in the synthesis of heteronuclear clusters. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/61775 10.32657/10356/61775 en 184 p. application/pdf
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic DRNTU::Science
spellingShingle DRNTU::Science
Liu, Yu
The [M(NHC)] (M=Pd, Pt) fragment in the synthesis of heteronuclear clusters
description While heteronuclear clusters having phosphine ligands are well-known, those containing nitrogen heterocyclic carbenes (NHCs) seem less explored. This describes work on the synthesis and characterization of new heteronuclear clusters of the heavier groups 8 (Ru and Os) and 10 (Pd and Pt) metals containing nitrogen heterocyclic carbenes (NHC). The reactivity of the [M(NHC)] (where M = Pd or Pt) synthon with various group 8 metal carbonyl clusters afforded a new synthetic methodology for such heterometallic clusters. A number of these clusters have been prepared and fully characterized, and their stability and reactivity investigated. A reasonable mechanism for their formation, supported by computational studies, has been proposed. In the course of this study, it was found that the reaction of free NHCs with the osmium carbonyl cluster Os3(CO)12 afforded a stable, zwitterionic, acyl metalate cluster. This cluster has been isolated and fully characterized, including by an X-ray crystallographic study, and it has been shown to lead to an NHC-substituted cluster. This represents the first direct structural evidence that nucleophilic substitution in carbonyl complexes involves initial nucleophilic attack at a carbonyl ligand.
author2 Leong Weng Kee
author_facet Leong Weng Kee
Liu, Yu
format Theses and Dissertations
author Liu, Yu
author_sort Liu, Yu
title The [M(NHC)] (M=Pd, Pt) fragment in the synthesis of heteronuclear clusters
title_short The [M(NHC)] (M=Pd, Pt) fragment in the synthesis of heteronuclear clusters
title_full The [M(NHC)] (M=Pd, Pt) fragment in the synthesis of heteronuclear clusters
title_fullStr The [M(NHC)] (M=Pd, Pt) fragment in the synthesis of heteronuclear clusters
title_full_unstemmed The [M(NHC)] (M=Pd, Pt) fragment in the synthesis of heteronuclear clusters
title_sort [m(nhc)] (m=pd, pt) fragment in the synthesis of heteronuclear clusters
publishDate 2014
url https://hdl.handle.net/10356/61775
_version_ 1759853996564021248