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Subvalent Cluster Compounds and Synthesis in Alternative Reaction Media
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry. (Oorganik kemi Prof. Lars Kloo)
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 [en]
metal cluster, Zintl ion, metal-organic 'sandwich' complex, ionic liquid, X-ray diffraction, spectroscopy, crystal structure
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-107218ISBN: 978-91-7501-579-8 (print)OAI: oai:DiVA.org:kth-107218DiVA: diva2:575637
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
List of papers
1. Dichloromethane as solvent for the synthesis of polycationic clusters at room temperature: a link to standard organometallic chemistry
Open this publication in new window or tab >>Dichloromethane as solvent for the synthesis of polycationic clusters at room temperature: a link to standard organometallic 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.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-26830 (URN)10.1039/c0dt00769b (DOI)000281230700003 ()2-s2.0-77955943287 (Scopus ID)
Note
QC 20101207Available from: 2010-12-07 Created: 2010-11-29 Last updated: 2017-12-11Bibliographically approved
2. Synthesis and characterization of binuclear palladium(I) compounds and the influence of competing arenes
Open this publication in new window or tab >>Synthesis and characterization of binuclear palladium(I) compounds and the influence of competing arenes
2010 (English)In: Journal of Organometallic Chemistry, ISSN 0022-328X, E-ISSN 1872-8561, Vol. 695, no 10-11, 1513-1517 p.Article in journal (Refereed) Published
Abstract [en]

The binuclear palladium(I) compounds, [Pd-2(Ga2Cl7)(2)(C7H8)(2)] (1), [Pd-2(GaCl4)(2)(C9H12)(2)]center dot C9H12 (2) and [Pd-2(Ga2Cl7)(2)(C6H5Cl)(2)] (3), have been prepared from palladium(II) chloride in gallium(III) chloride-arene reaction media. All isolated crystalline solids (1, 2 and 3) have been structurally characterized by single crystal X-ray diffraction and Raman spectroscopy. The results form quantum chemical calculations on the interaction energies of the arenes and the dipalladium unit of these compounds is also presented.

Keyword
Palladium, Gallium chloride, Arenes, Binuclear compounds, Crystal structure
National Category
Inorganic Chemistry Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-27877 (URN)10.1016/j.jorganchem.2010.03.011 (DOI)000277652500012 ()2-s2.0-77953288788 (Scopus ID)
Funder
Swedish Research Council
Note

QC 20110110

Available from: 2011-01-10 Created: 2011-01-03 Last updated: 2017-12-11Bibliographically approved
3. Structural Investigation of a Fully Ordered closo-Ge(9)(2-) Cluster in the Compound [K(+)(2,2,2-crypt)](2)Ge(9)(2-)
Open this publication in new window or tab >>Structural Investigation of a Fully Ordered closo-Ge(9)(2-) Cluster in the Compound [K(+)(2,2,2-crypt)](2)Ge(9)(2-)
2011 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 26, 3999-4005 p.Article in journal (Refereed) Published
Abstract [en]

[K(+)(2,2,2-crypt)] (2)Ge(9)(2-) containing the deltahedral Zintl anion Ge(9)(2-) has been isolated from a solution of K(4)Ge(9) in ethylenediamine in the presence of 2,2,2-crypt, intended as an intermediate in mixed-cluster synthesis. The subsequent crystallographic characterisation shows the closo-Ge(9)(2-) cluster unit to be tricapped trigonal-prismatic with a symmetry very close to D(3h). Each Ge(9)(2-) unit is surrounded by two 2,2,2-crypt units, each with a chelated K(+) cation, viz. [K(+)(2,2,2-crypt)]. The structure characterisation of this ordered Ge(9)(2-) cluster is surprisingly enough the first one reported. A chemical bonding analysis reveals two local minima of D(3h) symmetry, with that of lowest energy being highly similar to that resulting from the crystallographic analysis of low-temperature data. The cluster interaction scheme is based on highly delocalised bonding.

Keyword
Germanium, Zintl anions, Cluster compounds, X-ray diffraction, Cryptands
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-45286 (URN)10.1002/ejic.201100447 (DOI)000295265400025 ()2-s2.0-80052436785 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20111028Available from: 2011-10-28 Created: 2011-10-28 Last updated: 2017-12-08Bibliographically approved
4. Room-Temperature Synthesis of the Bi-5[GaCl4](3) Salt From Three Different Classes of Ionic Liquids
Open this publication in new window or tab >>Room-Temperature Synthesis of the Bi-5[GaCl4](3) Salt From Three Different Classes of Ionic Liquids
2013 (English)In: Journal of cluster science, ISSN 1040-7278, E-ISSN 1572-8862, Vol. 24, no 1, 157-164 p.Article in journal (Refereed) Published
Abstract [en]

Following the development in the synthesis of subvalent cluster compounds, we report on the use of three different classes of room-temperature ionic liquids for the synthesis of the pentabismuth-tris(tetragallate) salt, Bi-5[GaCl4](3), characterized by X-ray diffraction. The Bi-5[GaCl4](3) salt was prepared by reduction of BiCl3 using gallium metal in ionic liquid reaction media containing a strong Lewis acid, GaCl3. The ionic liquids; trihexyltetradecyl phosphonium chloride [Th-Td-P+]Cl-, 1-dodecyl-3-methylimidazolium chloride [Dod-Me-Im(+)]Cl- and N-butyl-N-methylpyrrolidinium chloride [Bu-Me-Pyrr(+)]Cl- from three of the main classes of ionic liquids were used in synthesis. Reactions using ionic liquids composed of the trihexyltetradecyl phosphonium cation [Th-Td-P+] and the anions; tetrafluoroborate [BF4 (-)], bis(trifluoro-methyl sulfonyl) imide [(Tf)(2)N-] and hexafluorophosphate [PF6 (-)] were also investigated.

Keyword
Bismuth, Polycation, Cluster compounds, Ionic liquids, X-ray diffraction
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:kth:diva-107394 (URN)10.1007/s10876-012-0526-3 (DOI)000314678500015 ()2-s2.0-84873742307 (Scopus ID)
Funder
Swedish Research Council
Note

QC 20130315

Available from: 2012-12-11 Created: 2012-12-11 Last updated: 2017-12-07Bibliographically approved
5. Arsenic Clusters in Solution: An Experimental and A Priori Theoretical EXAFS Study
Open this publication in new window or tab >>Arsenic Clusters in Solution: An Experimental and A Priori Theoretical EXAFS Study
(English)Manuscript (preprint) (Other academic)
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:kth:diva-107396 (URN)
Note

QS 2012

Available from: 2012-12-11 Created: 2012-12-11 Last updated: 2012-12-12Bibliographically approved
6. Tungsten Chloride W3Cl10(CH3CN)3 fromRoom-temperature Synthesis in Ionic liquid using an Organic Co-solvent
Open this publication in new window or tab >>Tungsten Chloride W3Cl10(CH3CN)3 fromRoom-temperature Synthesis in Ionic liquid using an Organic Co-solvent
(English)Manuscript (preprint) (Other academic)
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:kth:diva-107398 (URN)
Note

QS 2012

Available from: 2012-12-11 Created: 2012-12-11 Last updated: 2012-12-12Bibliographically approved

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