Synthesis of novel nanometric clusters by controlled oxidation of negatively-charged metal species
Lead Research Organisation:
University of Oxford
Department Name: Oxford Chemistry
Abstract
The focus of this proposal is to provide a detailed study of the behaviour of a series of naked anionic metal ions and clusters in solution and to employ them as synthons towards the isolation of novel nanometric clusters and molecular alloys. Controlled reduction of cationic metal species in solution is frequently employed as a route towards the synthesis of novel metal clusters and nanoparticles despite suffering from problems associated with sample purity and/or dispersity. Interestingly, an inverse approach, involving the oxidation of negatively-charged metal species in solution has yet to be exploited as a course towards cluster and nanoparticle synthesis. These anionic species can be obtained by direct dissolution of certain elements in solvents such as liquid ammonia or ethylenediamine in the presence of alkali metals, or alternatively by dissolution of preformed precursor alloys synthesized at high-temperature in the solid-state. Our research will focus on the solution reactivity of a series of such anionic species, namely anionic gold and silver, cesium platinide and the Zintl ions of groups 14 and 15. We envision that controlled oxidation of these species with transition metal reagents and post-transition metal and main-group organometallics will yield a wealth of new nanometric cluster species. The interest in such species arises due to the current size-limitation of our understanding of chemical bonding. As cluster nuclearity increases (n>12) and cluster shapes deviate from spherical geometries it is often found that such species fail to obey traditional rules for bonding in electron-deficient clusters. The systematic characterization of a greater breadth of large metalloid clusters is necessary if we are to form an understanding of the factors governing bonding at the nanometric scale and subsequently develop novel theories in order to account for the singularity of such systems.
Organisations
People |
ORCID iD |
Jose Goicoechea (Principal Investigator) |
Publications
Knapp CM
(2012)
[Co(?5-P5){?2-P2H(mes)}]2-: a phospha-organometallic complex obtained by the transition-metal-mediated activation of the heptaphosphide trianion.
in Angewandte Chemie (International ed. in English)
Denning MS
(2008)
[Hg(3)(Ge(9))(4)](10-): a nanometric molecular rod precursor to polymeric mercury-linked cluster chains.
in Dalton transactions (Cambridge, England : 2003)
Zhou B
(2009)
[Pb9CdCdPb9]6-: a Zintl cluster anion with an unsupported cadmium-cadmium bond.
in Chemical communications (Cambridge, England)
Zhou B
(2011)
A highly distorted open-shell endohedral Zintl cluster: [Mn@Pb12]3-.
in Inorganic chemistry
Knapp CM
(2011)
A versatile salt-metathesis route to heteroatomic clusters derived from phosphorus and arsenic Zintl anions.
in Dalton transactions (Cambridge, England : 2003)
Turbervill RS
(2014)
From clusters to unorthodox pnictogen sources: solution-phase reactivity of [E7](3-) (E = P-Sb) anions.
in Chemical reviews
Hansen D
(2012)
Further studies into the reactivity and coordination chemistry of [Ge9]4- Zintl ions. The indium-containing anions [In(Ge9)2]5-, [(Ge9)2In(C6H5)]4- and [Ge9{In(C6H5)3}2]4-
in Journal of Organometallic Chemistry