Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution

Johan Blixt, Julius Glaser, Jànos Mink, J. Mink, Per Persson, Magnus Sandström

Research output: Contribution to journalArticle

62 Citations (Scopus)

Abstract

The structures of the hydrated thallium(III) halide and pseudohalide complexes, [TlXn(OH2)m](3-n)+, X = Cl, Br, CN, in aqueous solution have been studied by a combination of X-ray absorption fine structure spectroscopy (XAFS), large-angle X-ray scattering (LAXS), and vibrational spectroscopic (Raman and IR) techniques including far-infrared studies of aqueous solutions and some solid phases with known structures. The vibrational Tl-X frequencies of all complexes are reported, force constants are calculated using normal coordinate analysis, and assignments are given. The structural results are consistent with octahedral six-coordination for the cationic complexes Tl(OH2)63+, TlX(OH2)52+, and trans-TlX2(OH2)4+. The coordination geometry changes to trigonal bipyramidal for the neutral TlBr3(OH2)2 complex and possibly also for TlCl3(OH2)2. The TlX4- complexes are all tetrahedral. Higher chloride complexes, TlCl5(OH2)2- and TlCl63-, are formed and have again octahedral coordination geometry. For the first and second halide complexes, TlX(OH2)52+ and TlX2(OH2)4+, no lengthening was found of the Tl-X bonds, with Tl-Br distances of 2.50(2) and 2.49(2) Å, respectively, and Tl-Cl distances of 2.37(2) Å for both complexes. The mean Tl-O bond distances increase slightly, ≈0.04 Å, from that of the Tl(OH2)63+ ion, at the formation of the first thallium(III) halide complexes. A further, more pronounced lengthening of about 0.1 Å occurs when the second complex forms, and it can be related to the relatively high bond strength in the trans-XTlX entity, which also is manifested through the Tl-X stretching force constants. For the recently established Tl(CN)n(3-n)+ complexes with no previously available structural information, the Tl-C distances were determined to be 2.11(2), 2.15(2), and 2.19-(2) Å for n = 2, 3, and 4, respectively. The Tl(CN)2+ complex has a linear structure, and the Tl(CN)4- complex is tetrahedral with the CN- ligands linearly coordinated. The lower complexes (n = 1-3) are hydrated, although the coordination numbers could not be unambiguously determined. A well-defined second coordination sphere corresponding to at least eight water molecules at a Tl-OII distance of ≈4.3 Å was found around the second complex, probably trans-Tl(CN)2(OH2)4+. The third cyano complex is probably pseudotetrahedral, Tl(CN)3(OH2). The bonding in the hexahydrated Tl3+ and Hg2+ ions is discussed, and differences in the mean M-O bond lengths, determined by the LAXS and EXAFS techniques, are interpreted as being due to an occurrence of two different sets of M-O distances in the first hydration shell.

Original languageEnglish
Pages (from-to)5089-5104
Number of pages16
JournalJournal of the American Chemical Society
Volume117
Issue number18
Publication statusPublished - May 10 1995

Fingerprint

Thallium
Cyanides
X ray scattering
Bromides
Chlorides
X ray absorption fine structure spectroscopy
X-Rays
Ions
Geometry
Bond length
Hydration
Stretching
Coordination Complexes
Ligands
Infrared radiation
Molecules
Water
Spectrum Analysis
thallium chloride

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Blixt, J., Glaser, J., Mink, J., Mink, J., Persson, P., & Sandström, M. (1995). Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution. Journal of the American Chemical Society, 117(18), 5089-5104.

Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution. / Blixt, Johan; Glaser, Julius; Mink, Jànos; Mink, J.; Persson, Per; Sandström, Magnus.

In: Journal of the American Chemical Society, Vol. 117, No. 18, 10.05.1995, p. 5089-5104.

Research output: Contribution to journalArticle

Blixt, J, Glaser, J, Mink, J, Mink, J, Persson, P & Sandström, M 1995, 'Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution', Journal of the American Chemical Society, vol. 117, no. 18, pp. 5089-5104.
Blixt, Johan ; Glaser, Julius ; Mink, Jànos ; Mink, J. ; Persson, Per ; Sandström, Magnus. / Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution. In: Journal of the American Chemical Society. 1995 ; Vol. 117, No. 18. pp. 5089-5104.
@article{187d646f83db4008b90b32bc8c523746,
title = "Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution",
abstract = "The structures of the hydrated thallium(III) halide and pseudohalide complexes, [TlXn(OH2)m](3-n)+, X = Cl, Br, CN, in aqueous solution have been studied by a combination of X-ray absorption fine structure spectroscopy (XAFS), large-angle X-ray scattering (LAXS), and vibrational spectroscopic (Raman and IR) techniques including far-infrared studies of aqueous solutions and some solid phases with known structures. The vibrational Tl-X frequencies of all complexes are reported, force constants are calculated using normal coordinate analysis, and assignments are given. The structural results are consistent with octahedral six-coordination for the cationic complexes Tl(OH2)63+, TlX(OH2)52+, and trans-TlX2(OH2)4+. The coordination geometry changes to trigonal bipyramidal for the neutral TlBr3(OH2)2 complex and possibly also for TlCl3(OH2)2. The TlX4- complexes are all tetrahedral. Higher chloride complexes, TlCl5(OH2)2- and TlCl63-, are formed and have again octahedral coordination geometry. For the first and second halide complexes, TlX(OH2)52+ and TlX2(OH2)4+, no lengthening was found of the Tl-X bonds, with Tl-Br distances of 2.50(2) and 2.49(2) {\AA}, respectively, and Tl-Cl distances of 2.37(2) {\AA} for both complexes. The mean Tl-O bond distances increase slightly, ≈0.04 {\AA}, from that of the Tl(OH2)63+ ion, at the formation of the first thallium(III) halide complexes. A further, more pronounced lengthening of about 0.1 {\AA} occurs when the second complex forms, and it can be related to the relatively high bond strength in the trans-XTlX entity, which also is manifested through the Tl-X stretching force constants. For the recently established Tl(CN)n(3-n)+ complexes with no previously available structural information, the Tl-C distances were determined to be 2.11(2), 2.15(2), and 2.19-(2) {\AA} for n = 2, 3, and 4, respectively. The Tl(CN)2+ complex has a linear structure, and the Tl(CN)4- complex is tetrahedral with the CN- ligands linearly coordinated. The lower complexes (n = 1-3) are hydrated, although the coordination numbers could not be unambiguously determined. A well-defined second coordination sphere corresponding to at least eight water molecules at a Tl-OII distance of ≈4.3 {\AA} was found around the second complex, probably trans-Tl(CN)2(OH2)4+. The third cyano complex is probably pseudotetrahedral, Tl(CN)3(OH2). The bonding in the hexahydrated Tl3+ and Hg2+ ions is discussed, and differences in the mean M-O bond lengths, determined by the LAXS and EXAFS techniques, are interpreted as being due to an occurrence of two different sets of M-O distances in the first hydration shell.",
author = "Johan Blixt and Julius Glaser and J{\`a}nos Mink and J. Mink and Per Persson and Magnus Sandstr{\"o}m",
year = "1995",
month = "5",
day = "10",
language = "English",
volume = "117",
pages = "5089--5104",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "18",

}

TY - JOUR

T1 - Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution

AU - Blixt, Johan

AU - Glaser, Julius

AU - Mink, Jànos

AU - Mink, J.

AU - Persson, Per

AU - Sandström, Magnus

PY - 1995/5/10

Y1 - 1995/5/10

N2 - The structures of the hydrated thallium(III) halide and pseudohalide complexes, [TlXn(OH2)m](3-n)+, X = Cl, Br, CN, in aqueous solution have been studied by a combination of X-ray absorption fine structure spectroscopy (XAFS), large-angle X-ray scattering (LAXS), and vibrational spectroscopic (Raman and IR) techniques including far-infrared studies of aqueous solutions and some solid phases with known structures. The vibrational Tl-X frequencies of all complexes are reported, force constants are calculated using normal coordinate analysis, and assignments are given. The structural results are consistent with octahedral six-coordination for the cationic complexes Tl(OH2)63+, TlX(OH2)52+, and trans-TlX2(OH2)4+. The coordination geometry changes to trigonal bipyramidal for the neutral TlBr3(OH2)2 complex and possibly also for TlCl3(OH2)2. The TlX4- complexes are all tetrahedral. Higher chloride complexes, TlCl5(OH2)2- and TlCl63-, are formed and have again octahedral coordination geometry. For the first and second halide complexes, TlX(OH2)52+ and TlX2(OH2)4+, no lengthening was found of the Tl-X bonds, with Tl-Br distances of 2.50(2) and 2.49(2) Å, respectively, and Tl-Cl distances of 2.37(2) Å for both complexes. The mean Tl-O bond distances increase slightly, ≈0.04 Å, from that of the Tl(OH2)63+ ion, at the formation of the first thallium(III) halide complexes. A further, more pronounced lengthening of about 0.1 Å occurs when the second complex forms, and it can be related to the relatively high bond strength in the trans-XTlX entity, which also is manifested through the Tl-X stretching force constants. For the recently established Tl(CN)n(3-n)+ complexes with no previously available structural information, the Tl-C distances were determined to be 2.11(2), 2.15(2), and 2.19-(2) Å for n = 2, 3, and 4, respectively. The Tl(CN)2+ complex has a linear structure, and the Tl(CN)4- complex is tetrahedral with the CN- ligands linearly coordinated. The lower complexes (n = 1-3) are hydrated, although the coordination numbers could not be unambiguously determined. A well-defined second coordination sphere corresponding to at least eight water molecules at a Tl-OII distance of ≈4.3 Å was found around the second complex, probably trans-Tl(CN)2(OH2)4+. The third cyano complex is probably pseudotetrahedral, Tl(CN)3(OH2). The bonding in the hexahydrated Tl3+ and Hg2+ ions is discussed, and differences in the mean M-O bond lengths, determined by the LAXS and EXAFS techniques, are interpreted as being due to an occurrence of two different sets of M-O distances in the first hydration shell.

AB - The structures of the hydrated thallium(III) halide and pseudohalide complexes, [TlXn(OH2)m](3-n)+, X = Cl, Br, CN, in aqueous solution have been studied by a combination of X-ray absorption fine structure spectroscopy (XAFS), large-angle X-ray scattering (LAXS), and vibrational spectroscopic (Raman and IR) techniques including far-infrared studies of aqueous solutions and some solid phases with known structures. The vibrational Tl-X frequencies of all complexes are reported, force constants are calculated using normal coordinate analysis, and assignments are given. The structural results are consistent with octahedral six-coordination for the cationic complexes Tl(OH2)63+, TlX(OH2)52+, and trans-TlX2(OH2)4+. The coordination geometry changes to trigonal bipyramidal for the neutral TlBr3(OH2)2 complex and possibly also for TlCl3(OH2)2. The TlX4- complexes are all tetrahedral. Higher chloride complexes, TlCl5(OH2)2- and TlCl63-, are formed and have again octahedral coordination geometry. For the first and second halide complexes, TlX(OH2)52+ and TlX2(OH2)4+, no lengthening was found of the Tl-X bonds, with Tl-Br distances of 2.50(2) and 2.49(2) Å, respectively, and Tl-Cl distances of 2.37(2) Å for both complexes. The mean Tl-O bond distances increase slightly, ≈0.04 Å, from that of the Tl(OH2)63+ ion, at the formation of the first thallium(III) halide complexes. A further, more pronounced lengthening of about 0.1 Å occurs when the second complex forms, and it can be related to the relatively high bond strength in the trans-XTlX entity, which also is manifested through the Tl-X stretching force constants. For the recently established Tl(CN)n(3-n)+ complexes with no previously available structural information, the Tl-C distances were determined to be 2.11(2), 2.15(2), and 2.19-(2) Å for n = 2, 3, and 4, respectively. The Tl(CN)2+ complex has a linear structure, and the Tl(CN)4- complex is tetrahedral with the CN- ligands linearly coordinated. The lower complexes (n = 1-3) are hydrated, although the coordination numbers could not be unambiguously determined. A well-defined second coordination sphere corresponding to at least eight water molecules at a Tl-OII distance of ≈4.3 Å was found around the second complex, probably trans-Tl(CN)2(OH2)4+. The third cyano complex is probably pseudotetrahedral, Tl(CN)3(OH2). The bonding in the hexahydrated Tl3+ and Hg2+ ions is discussed, and differences in the mean M-O bond lengths, determined by the LAXS and EXAFS techniques, are interpreted as being due to an occurrence of two different sets of M-O distances in the first hydration shell.

UR - http://www.scopus.com/inward/record.url?scp=0000418458&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000418458&partnerID=8YFLogxK

M3 - Article

VL - 117

SP - 5089

EP - 5104

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 18

ER -