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- Jalilehvand, F. (author)
Structure studies of dimeric Pt-2(CN)(10) (4-) pentacyanoplatinum(III) and monomeric pentacyanoplatinum(IV) complexes by EXAFS, vibrational spectroscopy, and X-ray crystallography
- Article/chapterEnglish2002
Publisher, publication year, extent ...
- 2002-03-08
- American Chemical Society (ACS),2002
- printrdacarrier
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- LIBRIS-ID:oai:DiVA.org:kth-21469
- https://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-21469URI
- https://doi.org/10.1021/jp012712xDOI
Supplementary language notes
- Language:English
- Summary in:English
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- QC 20100525
- The Structures of the dimeric bispentacyanoplatinate (III) (Pt-Pt) complex [Pt-2(CN)(10)](4-) and the pentacyanoplatinuni(IV) species [Pt(CN)(5)(OH)](2-), [Pt(CN)(5)(H2O)](-), and [Pt(CN)(5)I](2-) have been studied in aqueous solution by the EXAFS technique. A nonsupported Pt-Pt bond, 2.73(l) Angstrom, 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 [Pt-2(CN)(10)](4-) Complex, the [(NC)(5)Pt-TI(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)(5)X](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 Tl-2[Pt(CN)(5)(OH)] and K-2[Pt(CN)(5)I].0.6H(2)O 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)(5)I](2)- complex is 2.676(2) Angstrom in the crystal structure and 2.66(1) Angstrom 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.
Subject headings and genre
- metal-metal bond
- platinum-thallium compounds
- aqueous-solution
- chain
- scattering
- chemistry
- trivalent
- crystal
- ions
Added entries (persons, corporate bodies, meetings, titles ...)
- Maliarik, M. (author)
- Mink, J. (author)
- Sandstrom, M. (author)
- Ilyukhin, A. (author)
- Glaser, JuliusKTH,Kemi(Swepub:kth)u13oy1f4 (author)
- KTHKemi (creator_code:org_t)
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- In:Journal of Physical Chemistry A: American Chemical Society (ACS)106:14, s. 3501-35161089-56391520-5215
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