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Geometric and Electronic Structure of Metal-Metal Bonded Systems
KTH, School of Chemical Science and Engineering (CHE), Chemistry.ORCID iD: 0000-0001-6737-8233
2005 (English)Doctoral thesis, comprehensive summary (Other scientific)
Place, publisher, year, edition, pages
2005.
Keyword [en]
Inorganic chemistry
Keyword [sv]
Oorganisk kemi
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-197ISBN: 91-7178-036-X (print)OAI: oai:DiVA.org:kth-197DiVA: diva2:7876
Public defence
2005-05-20, K1, Kemi, Teknikringen 56, Stockholm, 13:00
Opponent
Supervisors
Available from: 2005-05-15 Created: 2005-05-15 Last updated: 2012-03-21
List of papers
1. Metal Iodides in Polyiodide Networks -The Structural Chemistry of Complex Gold Iodides with Excess of Iodine
Open this publication in new window or tab >>Metal Iodides in Polyiodide Networks -The Structural Chemistry of Complex Gold Iodides with Excess of Iodine
1999 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 5, no 1, 305-311 p.Article in journal (Refereed) Published
Abstract [en]

Theoretical calculations that compare the Ij ion and the [AuI4](-) ion show that they are closely related and have potential energy surface (PES) minima corresponding to an L-shaped structure. These calculations also indicate that the I-3(-) and [AuI2](-) ions should be exchangeable. These results were confirmed by the synthesis of the compounds (Et3S)[AuI4]. 2I(2) (1) and (Me3S)(2)[AuI4][I-3] (4), which have been characterised by X-ray diffraction, Raman and far-IR spectroscopy. The structure of 1 is made up of [AuI4](-) units coordinated by infinite zig-zag chains of I, molecules, and can be regarded as [AuI4](-) ions incorporated into a polyiodide network. The structure of 4 is closely related to those of the compounds of the M2Au2X6 family (M = Cs+, Rb+, NH4+, K+; X = Cl-, Br-, I-) which consist of square-planar [AuX4](-) and linear [AuX2](-) ions. However, in the structure of 4, the [AuX2](-) ions are replaced by IS ions.

Keyword
ab initio calculations, gold, iodine, quantum-chemical calculations, structure elucidation, vibrational analysis
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-5103 (URN)10.1002/(SICI)1521-3765(19990104)5:1<305::AID-CHEM305>3.0.CO;2-8 (DOI)000078024200031 ()
Note
QC 20101011Available from: 2005-05-15 Created: 2005-05-15 Last updated: 2017-12-04Bibliographically approved
2. Hard Acid and Soft Base Stabilisation of Di- and Trimercury Cations in Benzene Solution - A Spectroscopic, X-ray Scattering, and Quantum Chemical Study
Open this publication in new window or tab >>Hard Acid and Soft Base Stabilisation of Di- and Trimercury Cations in Benzene Solution - A Spectroscopic, X-ray Scattering, and Quantum Chemical Study
Show others...
1999 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 4, 633-642 p.Article in journal (Refereed) Published
Abstract [en]

Hg2Cl2 dissolves in GaCl3/benzene solution to yield Hg-2(2+) and chlorogallate(III) ions, GanCl3n+1-. In such solutions, Hg-2(2+) can be reduced to Hg-3(2+) by metallic mercury. Solubility measurements show that one mol of Hg is oxidised per mol of Hg-2(2+). The Hg-3(2+) ion gives a strong band at 110 cm(-1) in the Raman spectrum and Hg-Hg correlations at about 2.60 and 5.15 Angstrom in the radial distribution function obtained by Liquid X-ray scattering. - Hg-3(2+) can also be synthesised in high yield by direct oxidation of metallic mercury by Ga-III in GaCl3/benzene solution. In contrast, mercury is insoluble in neat Liquid GaCl3 and only sparingly soluble in GaCl3/KCl melts. It therefore seems likely that the thermodynamic stabilisation of subvalent mercury species in benzene solution not only relies on the traditional acid stabilisation provided by the hard Lewis acid GaCl3, but also on a "soft-base stabilisation" provided by interactions between the aromatic molecules and the cations. Evidence for such specific interactions between Hg-m(2+) cations and C6H6 are observed in the Raman spectra: The totally symmetric C6H6 band at 991 cm(-1) is found to split in the presence of Hg-m(2+) ions and to give new peaks at 978 (m = 2) and 982 (m = 3) cm(-1). - In order to further elucidate the cluster-arene interactions, ab initio and density functional calculations were performed for the model compounds Hg-m(C6H6)(2)(2+) and HgmCl2(C6H6)(2), m = 2 and 3. The calculations show that both models represent coordinations modes which are feasible for Hg-m(2+) ions. However, the calculated vibrational frequencies for the Hg-m(C6H6)(2)(2+) models with eta(1)/quasi-eta(3) coordination of the benzene molecules along the Hg-Hg vector are most consistent with the body of experimental and literature data. The counterions are thus suggested to occupy secondary coordination sites.

Keyword
mercury cations, subvalent compounds, ab initio calculations, liquid X-ray scattering
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-5104 (URN)000079454900009 ()
Note
QC 20101011Available from: 2005-05-15 Created: 2005-05-15 Last updated: 2017-12-04Bibliographically approved
3. On the Intra- and Intermolecular Bonding in Polyiodides
Open this publication in new window or tab >>On the Intra- and Intermolecular Bonding in Polyiodides
2002 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 5, 1203-1209 p.Article in journal (Refereed) Published
Abstract [en]

The nature of intra- and intermolecular interactions of poly-iodides has been investigated by means of quantum chemical methods and structural statistical data. In the region of "secondary bonds" the interaction is adequately described in terms of covalent bonding accompanied by dispersion. At greater distances the interaction is dominated by ion-quadrupole interactions between ionic and neutral iodine building blocks of the polyiodide structures.

Keyword
Bond theory, Iodine, Polyhalides
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5105 (URN)10.1002/1099-0682(200205) (DOI)000175267800031 ()
Note
QC 20100924Available from: 2005-05-15 Created: 2005-05-15 Last updated: 2017-12-04Bibliographically approved
4. The nature of subvalent gallium and indium in aqueous media
Open this publication in new window or tab >>The nature of subvalent gallium and indium in aqueous media
2002 (English)In: Polyhedron, ISSN 0277-5387, E-ISSN 1873-3719, Vol. 21, no 5-6, 519-524 p.Article in journal (Refereed) Published
Abstract [en]

Subvalent gallium can exist in aqueous solutions as Ga-Ga bonded gallium(II) species stabilised by halide ligands in the form of the complex anions Ga2X62- (X = Cl, Br or I) whose formation and reactivity are discussed. Gallium(I) compounds and mixed valence compounds of gallium react vigorously with water, converting any Ga+ ions into Ga(III) products. Indium(I) is more tolerant of water, so that perchlorate and other non-complexing aqueous media can support In+ ions at concentrations up to 10(-3) mol l(-1) before disproportionation to In(0) and In(III) occurs. Subvalent indium concentrations of approximately 10(-1) mol l(-1) are attained in halogen acid solution, particularly HBr which yields red, solid InBr upon dilution. Spectroscopic data suggest the precursor is an In(II)-In(II) bromide complex (probably In2Br62-) capable of breaking up into In(I) and In(III) products.

Keyword
subvalent indium and gallium, gallium(II), indium(I), indium(II), halide complexes, Raman spectra
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5106 (URN)10.1016/S0277-5387(01)01030-0 (DOI)000175462300007 ()
Note
QC 20101004Available from: 2005-05-15 Created: 2005-05-15 Last updated: 2017-12-04Bibliographically approved
5. On the Solvation of the Mercury(I) Ion. A Structural, Vibration Spectroscopic and Quantum Chemical Study
Open this publication in new window or tab >>On the Solvation of the Mercury(I) Ion. A Structural, Vibration Spectroscopic and Quantum Chemical Study
2004 (English)In: Inorganica Chimica Acta, ISSN 0020-1693, E-ISSN 1873-3255, Vol. 357, no 9, 2624-2634 p.Article in journal (Refereed) Published
Abstract [en]

The structure of the solvated mercury(I) ion in solvents such as water, methanol, dimethylsulfoxide, N,N-dimethylpropyleneurea, acetonitrile and pyridine solution has been studied by means of EXAFS and/or large angle X-ray scattering (LAXS). Raman spectroscopy has been used for the determination of the Hg-Hg stretching frequencies. The Hg-Hg bond length increases with increasing solvating ability of the solvent, while the stretching frequency appears to be almost invariant. The results of quantum chemical calculations indicate a significant influence on the Hg-Hg bond from solvation. The structure of solid anhydrous mercury(I) trifluoromethanesulfonate, Hg 2(CF3SO3)2 (1), has been determined by powder diffraction methods. The structure comprises of discrete molecules, where each mercury binds to an oxygen atom in the anion, forming an almost linear O-Hg-Hg-O entity; the Hg-Hg-O angle is 173°and the Hg-Hg and Hg-O bond lengths are 2.486(6) and 2.099(22) Å, respectively.

Keyword
Ab initio calculations, EXAFS, Large angle X-ray scattering, Powder diffraction, Solvation models
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5107 (URN)10.1016/j.ica.2004.03.010 (DOI)000222745900025 ()2-s2.0-3042670197 (Scopus ID)
Note
QC 20100924Available from: 2005-05-15 Created: 2005-05-15 Last updated: 2017-12-04Bibliographically approved
6. Synthesis and Crystal Structures of Di- and Trimercury Chlorogallates
Open this publication in new window or tab >>Synthesis and Crystal Structures of Di- and Trimercury Chlorogallates
2004 (English)In: Zeitschrift für Anorganische und Allgemeines Chemie, ISSN 0044-2313, E-ISSN 1521-3749, Vol. 630, no 5, 760-762 p.Article in journal (Refereed) Published
Abstract [en]

Mercury(I) chloride reacts with gallium(III) chloride in benzene/1,2-dichlorobenzene solution to give the binuclear compound Hg-2(GaCl4)(2) (1). Reduction of mercury(I) chloride with mercury in gallium(III) chloride-benzene mixture leads to the trinuclear compound Hg-3(GaCl4)(2) (2). The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction {Hg-2(GaCl4)(2): triclinic, P (1) over bar, a = 645.21(3), b = 654.44(3), c = 927.17(7) pm, alpha = 83.526(2)degrees, beta = 74.915(2)degrees, gamma = 61.863(3)degrees; Hg-3(GaCl4)(2): monoclinic, P2(1)/c, a = 715.79(1), b = 1501.59(4), c = 1421.43(4) pm, beta = 98.9798(9)degrees}.

Keyword
mercury, gallium, crystal structure, subvalent compounds
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-5108 (URN)10.1002/zaac.200400015 (DOI)000221884100026 ()2-s2.0-4644302357 (Scopus ID)
Note
QC 20101001Available from: 2005-05-15 Created: 2005-05-15 Last updated: 2017-12-04Bibliographically approved
7. On the Structure of Sn9(4-) Cluster in Liquid and Solid State
Open this publication in new window or tab >>On the Structure of Sn9(4-) Cluster in Liquid and Solid State
2005 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 14, 2888-2894 p.Article in journal (Refereed) Published
Abstract [en]

The nonastannide clusters have been investigated usingEXAFS, NMR and Raman spectroscopy as well as quantum chemical calculations explicitly considering a model cationic field and solid-state statistics. NMR spectroscopic andEXAFS results are basically identical to those previously published and consistent with a fluctional model of the cluster. The quantum chemical calculations show that there is no significant difference in energy between the two model geometries, C4v and D3h, and that the vibrational frequencies are very low, clearly indicating that the cluster is expected to be fluctional. The solid-state statistics show that both model geometries can be used to describe all known nonastannide structures with reasonable success, illustrating that the classification of the nonastannide clusters in terms of specific symmetries is entirely arbitrary.

Keyword
EXAFS spectroscopy / Cluster compounds, Polyanions, Solid-state structures, Ab initio calculations
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-5109 (URN)10.1002/ejic.200500043 (DOI)000230781400015 ()2-s2.0-22444442431 (Scopus ID)
Note
QC 20101011Available from: 2005-05-15 Created: 2005-05-15 Last updated: 2017-12-04Bibliographically approved
8. On the Stability of Cd2(2+) and Zn2(2+) Ions. A Theoretical Study
Open this publication in new window or tab >>On the Stability of Cd2(2+) and Zn2(2+) Ions. A Theoretical Study
(English)Manuscript (Other academic)
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-5110 (URN)
Note
QC 20101011Available from: 2005-05-15 Created: 2005-05-15 Last updated: 2010-10-11Bibliographically approved

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