A New Class of Oligonuclear Platinum-Thallium Compounds with a DirectMetal2Metal Bond3. Unusual Equilibria in Aqueous Solution

M Maliarik, J Glaser, Imre Toth, Mateus Webba da Silva, L Zekany

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Abstract

A new series of four binuclear platinum-thallium cyano compoundscontaining a direct and unsupported by ligands metal2metalbond has been prepared in aqueous solution. Thesecompounds are represented by the formula[(NC)5Pt2Tl(CN)n21](n21)2 (n = 124 for compounds I, II, IIIIV, respectively) and [(NC)5Pt2Tl2Pt(CN)5]32 (for compoundV). The oligonuclear complexes are synthesised accordingto the reaction mPt(CN)422 + Tl3+ + nCN2 v [PtmTl-(CN)4m+n]322m2n. Thus, there occurs a change of the coordinationnumber of the Pt center from four (square planar) tosix (octahedral). Consequently, the formation of binuclearplatinum-thallium cyano compounds involves at least twosteps: (i) formation of metal2metal bond and (ii) formation of(NC)5Pt2 unit by a cyanide transfer process. 2 The complexes exist in an equilibrium, which also includes the parentcomplexes Pt(CN)422 and Tl(CN)n32n (n = 024), and can becontrolled by varying the cyanide concentration and/or pHof the solution. The stability constants of the compounds âN =[PtmTl(CN)4m+n322m2n] / {[Pt(CN)422]m· [Tl3+] ·[CN2]n} havebeen determined by means of multinuclear NMR (195Pt,205Tl): logâN = 19.9±0.4, 30.7±0.3, 38.6±0.3, and 44.8±0.2 forI, II, III, and IV (m = 1, n = 124), and 32.1±0.3 for V (m = 2,n = 2), respectively, (in 1 M NaClO4 as ionic medium, at 25oC). To our knowledge, the present work constitutes the firstdetailed equilibrium study of metal2metal bonded compounds;it indicates that also other cluster formation reactionsdescribed in the literature may represent real equilibria.
LanguageEnglish
Pages565-570
JournalEuropean Journal of Inorganic Chemistry
Volume1998
Publication statusPublished - 1998

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Thallium compounds
Cyanides
Platinum
Thallium
Nuclear magnetic resonance
Ligands

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@article{4be313a0589b46818c7f5f7ce8dd7656,
title = "A New Class of Oligonuclear Platinum-Thallium Compounds with a DirectMetal2Metal Bond3. Unusual Equilibria in Aqueous Solution",
abstract = "A new series of four binuclear platinum-thallium cyano compoundscontaining a direct and unsupported by ligands metal2metalbond has been prepared in aqueous solution. Thesecompounds are represented by the formula[(NC)5Pt2Tl(CN)n21](n21)2 (n = 124 for compounds I, II, IIIIV, respectively) and [(NC)5Pt2Tl2Pt(CN)5]32 (for compoundV). The oligonuclear complexes are synthesised accordingto the reaction mPt(CN)422 + Tl3+ + nCN2 v [PtmTl-(CN)4m+n]322m2n. Thus, there occurs a change of the coordinationnumber of the Pt center from four (square planar) tosix (octahedral). Consequently, the formation of binuclearplatinum-thallium cyano compounds involves at least twosteps: (i) formation of metal2metal bond and (ii) formation of(NC)5Pt2 unit by a cyanide transfer process. 2 The complexes exist in an equilibrium, which also includes the parentcomplexes Pt(CN)422 and Tl(CN)n32n (n = 024), and can becontrolled by varying the cyanide concentration and/or pHof the solution. The stability constants of the compounds {\^a}N =[PtmTl(CN)4m+n322m2n] / {[Pt(CN)422]m· [Tl3+] ·[CN2]n} havebeen determined by means of multinuclear NMR (195Pt,205Tl): log{\^a}N = 19.9±0.4, 30.7±0.3, 38.6±0.3, and 44.8±0.2 forI, II, III, and IV (m = 1, n = 124), and 32.1±0.3 for V (m = 2,n = 2), respectively, (in 1 M NaClO4 as ionic medium, at 25oC). To our knowledge, the present work constitutes the firstdetailed equilibrium study of metal2metal bonded compounds;it indicates that also other cluster formation reactionsdescribed in the literature may represent real equilibria.",
author = "M Maliarik and J Glaser and Imre Toth and {Webba da Silva}, Mateus and L Zekany",
year = "1998",
language = "English",
volume = "1998",
pages = "565--570",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",

}

A New Class of Oligonuclear Platinum-Thallium Compounds with a DirectMetal2Metal Bond3. Unusual Equilibria in Aqueous Solution. / Maliarik, M; Glaser, J; Toth, Imre; Webba da Silva, Mateus; Zekany, L.

In: European Journal of Inorganic Chemistry, Vol. 1998, 1998, p. 565-570.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A New Class of Oligonuclear Platinum-Thallium Compounds with a DirectMetal2Metal Bond3. Unusual Equilibria in Aqueous Solution

AU - Maliarik, M

AU - Glaser, J

AU - Toth, Imre

AU - Webba da Silva, Mateus

AU - Zekany, L

PY - 1998

Y1 - 1998

N2 - A new series of four binuclear platinum-thallium cyano compoundscontaining a direct and unsupported by ligands metal2metalbond has been prepared in aqueous solution. Thesecompounds are represented by the formula[(NC)5Pt2Tl(CN)n21](n21)2 (n = 124 for compounds I, II, IIIIV, respectively) and [(NC)5Pt2Tl2Pt(CN)5]32 (for compoundV). The oligonuclear complexes are synthesised accordingto the reaction mPt(CN)422 + Tl3+ + nCN2 v [PtmTl-(CN)4m+n]322m2n. Thus, there occurs a change of the coordinationnumber of the Pt center from four (square planar) tosix (octahedral). Consequently, the formation of binuclearplatinum-thallium cyano compounds involves at least twosteps: (i) formation of metal2metal bond and (ii) formation of(NC)5Pt2 unit by a cyanide transfer process. 2 The complexes exist in an equilibrium, which also includes the parentcomplexes Pt(CN)422 and Tl(CN)n32n (n = 024), and can becontrolled by varying the cyanide concentration and/or pHof the solution. The stability constants of the compounds âN =[PtmTl(CN)4m+n322m2n] / {[Pt(CN)422]m· [Tl3+] ·[CN2]n} havebeen determined by means of multinuclear NMR (195Pt,205Tl): logâN = 19.9±0.4, 30.7±0.3, 38.6±0.3, and 44.8±0.2 forI, II, III, and IV (m = 1, n = 124), and 32.1±0.3 for V (m = 2,n = 2), respectively, (in 1 M NaClO4 as ionic medium, at 25oC). To our knowledge, the present work constitutes the firstdetailed equilibrium study of metal2metal bonded compounds;it indicates that also other cluster formation reactionsdescribed in the literature may represent real equilibria.

AB - A new series of four binuclear platinum-thallium cyano compoundscontaining a direct and unsupported by ligands metal2metalbond has been prepared in aqueous solution. Thesecompounds are represented by the formula[(NC)5Pt2Tl(CN)n21](n21)2 (n = 124 for compounds I, II, IIIIV, respectively) and [(NC)5Pt2Tl2Pt(CN)5]32 (for compoundV). The oligonuclear complexes are synthesised accordingto the reaction mPt(CN)422 + Tl3+ + nCN2 v [PtmTl-(CN)4m+n]322m2n. Thus, there occurs a change of the coordinationnumber of the Pt center from four (square planar) tosix (octahedral). Consequently, the formation of binuclearplatinum-thallium cyano compounds involves at least twosteps: (i) formation of metal2metal bond and (ii) formation of(NC)5Pt2 unit by a cyanide transfer process. 2 The complexes exist in an equilibrium, which also includes the parentcomplexes Pt(CN)422 and Tl(CN)n32n (n = 024), and can becontrolled by varying the cyanide concentration and/or pHof the solution. The stability constants of the compounds âN =[PtmTl(CN)4m+n322m2n] / {[Pt(CN)422]m· [Tl3+] ·[CN2]n} havebeen determined by means of multinuclear NMR (195Pt,205Tl): logâN = 19.9±0.4, 30.7±0.3, 38.6±0.3, and 44.8±0.2 forI, II, III, and IV (m = 1, n = 124), and 32.1±0.3 for V (m = 2,n = 2), respectively, (in 1 M NaClO4 as ionic medium, at 25oC). To our knowledge, the present work constitutes the firstdetailed equilibrium study of metal2metal bonded compounds;it indicates that also other cluster formation reactionsdescribed in the literature may represent real equilibria.

M3 - Article

VL - 1998

SP - 565

EP - 570

JO - European Journal of Inorganic Chemistry

T2 - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

ER -