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Dichloromethane as solvent for the synthesis of polycationic clusters at room temperature: a link to standard organometallic chemistry
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry. (Oorganisk kemi, Lars Kloo)
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry.
2010 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 39, no 35, 8132-8134 p.Article in journal (Refereed) Published
Abstract [en]

Dichloromethane (DCM), CH2Cl2 has been identified as an alternative reaction medium for room-temperature synthesis of subvalent homopolyatomic clusters of the group 15 element bismuth.

Place, publisher, year, edition, pages
2010. Vol. 39, no 35, 8132-8134 p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-26830DOI: 10.1039/c0dt00769bISI: 000281230700003Scopus ID: 2-s2.0-77955943287OAI: oai:DiVA.org:kth-26830DiVA: diva2:375155
Note
QC 20101207Available from: 2010-12-07 Created: 2010-11-29 Last updated: 2017-12-11Bibliographically approved
In thesis
1. Subvalent Cluster Compounds and Synthesis in Alternative Reaction Media
Open this publication in new window or tab >>Subvalent Cluster Compounds and Synthesis in Alternative Reaction Media
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

With the aim of finding alternative reaction media for the synthesis of subvalent main group and transition metal cluster compounds, traditionally made through solid state reactions or in superacidic media, different alternative reaction media have been explored in this work. Room-temperature ionic liquids are amongst the more unconventional reaction media used. The syntheses performed have been aimed at both anionic and cationic cluster and the main tools used for characterization have been different X-ray diffraction and spectroscopic techniques.

Selected ionic liquids have along with dichloromethane been shown to work as alternative reaction media for room temperature synthesis of the Bi5[GaCl4]3 salt. The salt containing the subvalent naked bismuth polycation Bi5 3+ was isolated from reduction reactions of BiCl3 in Ga/GaCl3-dichloromethane respectively Ga/GaCl3-ioinc liquid media. Three different classes of ionic liquids based on phosphonium-, imidazolium- and pyrrolidinium- salts have been used in synthesis. Homopolyatomic clusters from the lighter Group 15 element arsenic have also been studied. Solutions from the oxidative and reductive reaction routes of arsenic and AsCl3 in Lewis acidic toluene media were studied by EXAFS spectroscopy. The results were evaluated using molecular dynamics simulations of arsenic clusters. A discussion on how the calculated As4 cluster model relates to the experimental data resulted from this study.

In terms of homopolyatomic anionic clusters the [K+(2,2,2-crypt)]2Ge9 2- compound containing the naked Ge9 2- anionic cluster has been isolated. The crystallographic investigation of [K+(2,2,2-crypt)]2Ge9 2- shows Zintl cluster anion Ge9 2- to be tricapped trigonal-prismatic with a symmetry very close to D3h. A chemical bonding analysis reveals two local minima of D3h symmetry and the cluster interaction scheme to be based on highly delocalised bonding.

Ligand supported transition metal clusters from tungsten and palladium have also been prepared. Reduction of WCl6 in a reaction mixture of ionic liquid and co-solvent toluene resulted in tritungsten decachloride; W3Cl10(MeCN)3, being formed. Furthermore, palladium sandwich compounds; [Pd2(Ga2Cl7)(C7H8)2], [Pd2(GaCl4)(C9H12)2]∙C9H12 and [Pd2(Ga2Cl7)(C6H5Cl)2] have been prepared using GaCl3-arene reaction media.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. vi, 72 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:64
Keyword
metal cluster, Zintl ion, metal-organic 'sandwich' complex, ionic liquid, X-ray diffraction, spectroscopy, crystal structure
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-107218 (URN)978-91-7501-579-8 (ISBN)
Public defence
2012-12-20, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council, B61416
Note

QC 20121212

Available from: 2012-12-12 Created: 2012-12-10 Last updated: 2012-12-12Bibliographically approved

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