Notizen: Das Schwingungsspektrum des Hexacyanoplatinat(IV)-ions

Siebert, Hans; Siebert, A.

doi:10.1515/znb-1967-0621

Cited by 11 publications

(4 citation statements)

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“…The fundamental modes, their potential energy distributions over the internal coordinates, and force constants for the best fit are given in Tables S4 and S5 (Supporting Information). For a consistency check, the [Pt(CN) 6 ] 2- complex was reevaluated from literature data, with results in satisfactory agreement with the previous investigation …”

Section: Methodssupporting

confidence: 57%

“…For a consistency check, the [Pt(CN)6] 2complex was reevaluated from literature data, with results in satisfactory agreement with the previous investigation. 24…”

Section: Methodsmentioning

confidence: 99%

“…In our previous paper, a Raman band which appeared at 2210 cm -1 was ascribed to the apical cyano ligand of the [(NC) 5 Pt−Tl(CN) n ] n - complexes. However, it was later found to originate from [Pt(CN) 6 ] 2- species, , formed as a result of a partial redox photodecomposition when the complexes were irradiated with high-energy 514.5 nm laser radiation from an argon ion laser. With the 1064 nm infrared laser line used in the present work, no C−N band was observed at frequencies higher than 2200 cm -1 for the dimetallic complexes in solution (cf.…”

Section: Methodsmentioning

confidence: 99%

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New Class of Oligonuclear Platinum−Thallium Compounds with a Direct Metal-Metal Bond. 5. Structure Determination of Heterodimetallic Cyano Complexes in Aqueous Solution by EXAFS and Vibrational Spectroscopy

et al. 2001

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The structures of three closely related heterodimetallic cyano complexes, [(NC)(5)Pt-Tl(CN)(n)()](n)()(-) (n = 1-3), formed in reactions between [Pt(II)(CN)(4)](2)(-) and Tl(III) cyano complexes, have been studied in aqueous solution. Multinuclear NMR data ((205)Tl, (195)Pt, and (13)C) were used for identification and quantitative analysis. X-ray absorption spectra were recorded at the Pt and Tl L(III) edges. The EXAFS data show, after developing a model describing the extensive multiple scattering within the linearly coordinated cyano ligands, short Pt-Tl bond distances in the [(NC)(5)Pt-Tl(CN)(n)()](n)()(-) complexes: 2.60(1), 2.62(1), and 2.64(1) A for n = 1-3, respectively. Thus, the Pt-Tl bond distance increases with increasing number of cyano ligands on the thallium atom. In all three complexes the thallium atom and five cyano ligands, with a mean Pt-C distance of 2.00-2.01 A, octahedrally coordinate the platinum atom. In the hydrated [(NC)(5)Pt-Tl(CN)(H(2)O)(4)](-) species the thallium atom coordinates one cyano ligand, probably as a linear Pt-Tl-CN entity with a Tl-C bond distance of 2.13(1) A, and possibly four loosely bound water molecules with a mean Tl-O bond distance of about 2.51 A. In the [(NC)(5)Pt-Tl(CN)(2)](2)(-) species, the thallium atom probably coordinates the cyano ligands trigonally with two Tl-C bond distances at 2.20(2) A, and in [(NC)(5)Pt-Tl(CN)(3)](3)(-) Tl coordinates tetrahedrally with three Tl-C distances at 2.22(2) A. EXAFS data were reevaluated for previously studied mononuclear thallium(III)-cyano complexes in aqueous solution, [Tl(CN)(2)(H(2)O)(4)](+), [Tl(CN)(3)(H(2)O)], and [Tl(CN)(4)](-), and also for the solid K[Tl(CN)(4)] compound. A comparison shows that the Tl-C bond distances are longer in the dinuclear complexes [(NC)(5)Pt-Tl(CN)(n)()](n)()(-) (n = 1-3) for the same coordination number. Relative oxidation states of the metal atoms were estimated from their (195)Pt and (205)Tl chemical shifts, confirming that the [(NC)(5)Pt-Tl(CN)(n)()](n)()(-) complexes can be considered as metastable intermediates in a two-electron-transfer redox reaction from platinum(II) to thallium(III). Vibrational spectra were recorded and force constants from normal-coordinate analyses are used for discussing the delocalized bonding in these species.

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Section: Methodssupporting

confidence: 57%

“…For a consistency check, the [Pt(CN)6] 2complex was reevaluated from literature data, with results in satisfactory agreement with the previous investigation. 24…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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New Class of Oligonuclear Platinum−Thallium Compounds with a Direct Metal-Metal Bond. 5. Structure Determination of Heterodimetallic Cyano Complexes in Aqueous Solution by EXAFS and Vibrational Spectroscopy

et al. 2001

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“…The equatorial C−N symmetric stretching (A 1g ) frequency (2192 cm -1 , Table ) for the [Pt III 2 (CN) 10 ] 4- complex, is intermediate between those of the [Pt II (CN) 4 ] 2- and the [Pt IV (CN) 6 ] 2- complexes, 2143.5 and 2211 cm -1 , respectively, , but is higher than those found for the partially oxidized compounds, e.g., 2182 cm -1 for K 2 [Pt II (CN) 4 ]Br 0.33 …”

Section: Discussionmentioning

confidence: 89%

Structure Studies of Dimeric [Pt₂(CN)₁₀]^4- Pentacyanoplatinum(III) and Monomeric Pentacyanoplatinum(IV) Complexes by EXAFS, Vibrational Spectroscopy, and X-ray Crystallography

et al. 2002

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The structures of the dimeric bispentacyanoplatinate(III)(PtPt) complex [Pt2(CN)10]4- and the pentacyanoplatinum(IV) species [Pt(CN)5(OH)]2-, [Pt(CN)5(H2O)]-, and [Pt(CN)5I]2- have been studied in aqueous solution by the EXAFS technique. A nonsupported Pt−Pt bond, 2.73(1) Å, connects two Pt(CN)5 entities in the dimer. Normal coordinate analyses have been made on the basis of the Raman spectra, and the force constants have been used for discussions of the bonding. The metal−metal stretching force constants for the [Pt2(CN)10]4- complex, the [(NC)5Pt−Tl(CN) n ] n - (n = 1, 2, and 3) complexes, and some other dimetallic complexes have been correlated with the metal−metal bond distances. In the [Pt(CN)5X] n - complexes, the mean Pt−C bond distance of the pentacyanoplatinum group was found to increase, and the corresponding Pt−C force constants were found to decrease, with increasing donor ability of the ligand X in the order X = H2O, OH, I, and Pt(CN)5. The crystal structures of the compounds Tl2[Pt(CN)5(OH)] and K2[Pt(CN)5I]·0.6H2O were determined by single-crystal X-ray diffraction techniques and used for comparisons with the EXAFS models. The Pt−I bond distance of the [Pt(CN)5I]2- complex is 2.676(2) Å in the crystal structure and 2.66(1) Å in solution by EXAFS. A method is described for estimating the force constant for the metal−metal bond stretch in dimetallic complexes with heavy metal atoms, based on the use of an effective “spectroscopic” mass of the metal atoms in a diatomic model. The 18-electron rule is found to be useful for rationalizing the structures of the metal−metal bonded cyano complexes and a guideline in searching for metal cyano complexes analogous to those currently described.

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Vibrational Spectra of Transition Metal Complexes and the Nature of the Metal‐Ligand Bond

James

Nolan

1967

Progress in Inorganic Chemistry

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Notizen: Das Schwingungsspektrum des Hexacyanoplatinat(IV)-ions

Cited by 11 publications

References 0 publications

New Class of Oligonuclear Platinum−Thallium Compounds with a Direct Metal-Metal Bond. 5. Structure Determination of Heterodimetallic Cyano Complexes in Aqueous Solution by EXAFS and Vibrational Spectroscopy

New Class of Oligonuclear Platinum−Thallium Compounds with a Direct Metal-Metal Bond. 5. Structure Determination of Heterodimetallic Cyano Complexes in Aqueous Solution by EXAFS and Vibrational Spectroscopy

Structure Studies of Dimeric [Pt₂(CN)₁₀]^4- Pentacyanoplatinum(III) and Monomeric Pentacyanoplatinum(IV) Complexes by EXAFS, Vibrational Spectroscopy, and X-ray Crystallography

Vibrational Spectra of Transition Metal Complexes and the Nature of the Metal‐Ligand Bond

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Notizen: Das Schwingungsspektrum des Hexacyanoplatinat(IV)-ions

Cited by 11 publications

References 0 publications

New Class of Oligonuclear Platinum−Thallium Compounds with a Direct Metal-Metal Bond. 5. Structure Determination of Heterodimetallic Cyano Complexes in Aqueous Solution by EXAFS and Vibrational Spectroscopy

New Class of Oligonuclear Platinum−Thallium Compounds with a Direct Metal-Metal Bond. 5. Structure Determination of Heterodimetallic Cyano Complexes in Aqueous Solution by EXAFS and Vibrational Spectroscopy

Structure Studies of Dimeric [Pt2(CN)10]4- Pentacyanoplatinum(III) and Monomeric Pentacyanoplatinum(IV) Complexes by EXAFS, Vibrational Spectroscopy, and X-ray Crystallography

Vibrational Spectra of Transition Metal Complexes and the Nature of the Metal‐Ligand Bond

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Structure Studies of Dimeric [Pt₂(CN)₁₀]^4- Pentacyanoplatinum(III) and Monomeric Pentacyanoplatinum(IV) Complexes by EXAFS, Vibrational Spectroscopy, and X-ray Crystallography