An X-ray absorption spectroscopic investigation of the geometry of Pt(IV) in H2PtCl6 ammonia solution

被引：7

作者：

Chen, Shuangming ^{[1
]}

Wu, Yanfei ^{[1
]}

Tao, Shi ^{[1
]}

Cui, Peixin ^{[1
]}

Chu, Wangsheng ^{[1
]}

Chen, Xing ^{[1
]}

Wu, Ziyu ^{[1
]}

机构：

[1] Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230029, Peoples R China

来源：

JOURNAL OF MOLECULAR STRUCTURE | 2013年 / 1041卷

关键词：

PtCl62-; Pt(NH3)(6)(4+); XANES; EXAFS; Local structure; NEAR-EDGE STRUCTURE; COMPLEXES; EXAFS; HEXACHLOROPLATINATE(IV);

D O I：

10.1016/j.molstruc.2013.02.044

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The geometrical structure of noble metal cations has an important impact in many areas. Therefore, the structure of some noble cations in solution has been investigated in order to understand the relationship between the structure and property of noble metal cations in solution. In this contribution, the coordination chemistry of H2PtCl6 in ammonia solution was investigated by X-ray absorption spectroscopy (XAS). We found that Cl ligands around Pt with a Pt-Cl bond length of 2.32 angstrom are completely replaced by NH3 ligands with a Pt-N distance of 2.05 angstrom. Theoretical calculations point out the occurrence of both a Pt-Cl and a Pt-N orbital hybridization. The observed 'hybridization peak' and the post-edge feature have been assigned to the contribution of Cl and N d-states. (C) 2013 Elsevier B.V. All rights reserved.

引用

页码：39 / 43

页数：5

共 21 条

[1] Hybridization peaks in Pt-Cl XANES [J].

Ankudinov, AL ;

Rehr, JJ ;

Bare, SR .

CHEMICAL PHYSICS LETTERS, 2000, 316 (5-6) :495-500

[2] Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure [J].

Ankudinov, AL ;

Ravel, B ;

Rehr, JJ ;

Conradson, SD .

PHYSICAL REVIEW B, 1998, 58 (12) :7565-7576

[3] Geometry and hydration structure of Pt(II) square planar complexes [Pt(H2O)4]2+ and [PtCl4]2- as studied by X-ray absorption spectroscopies and quantum-mechanical computations [J].

Ayala, R ;

Marcos, ES ;

Díaz-Moreno, S ;

Solé, VA ;

Muñoz-Páez, A .

JOURNAL OF PHYSICAL CHEMISTRY B, 2001, 105 (31) :7588-7593

[4] Unique stability of μ-hydroxo ligands in Pt(IV) complexes towards alkaline hydrolysis [J].

Beck, I. E. ;

Kriventsov, V. V. ;

Fedotov, M. A. ;

Bukhtiyarov, V. I. .

NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION A-ACCELERATORS SPECTROMETERS DETECTORS AND ASSOCIATED EQUIPMENT, 2009, 603 (1-2) :182-184

[5] MULTIPLE-SCATTERING REGIME AND HIGHER-ORDER CORRELATIONS IN X-RAY-ABSORPTION SPECTRA OF LIQUID SOLUTIONS [J].

BENFATTO, M ;

NATOLI, CR ;

BIANCONI, A ;

GARCIA, J ;

MARCELLI, A ;

FANFONI, M ;

DAVOLI, I .

PHYSICAL REVIEW B, 1986, 34 (08) :5774-5781

[6]

Bokii G.B., 1949, DOKL AKAD NAUK SSSR, V67, P73

[7] Axial Structure of the Pd(II) Aqua Ion in Solution [J].

Bowron, Daniel T. ;

Beret, Elizabeth C. ;

Martin-Zamora, Eloisa ;

Soper, Alan K. ;

Sanchez Marcos, Enrique .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (02) :962-967

[8] Correlation between local structure and molar ratio of Au (III) complexes in aqueous solution: An XAS investigation [J].

Chen, Xing ;

Chu, Wangsheng ;

Chen, Dongliang ;

Wu, Zhonghua ;

Marcelli, A. ;

Wu, Ziyu .

CHEMICAL GEOLOGY, 2009, 268 (1-2) :74-80

[9] Geometry of Pt(IV) in H2PtCl6 aqueous solution: An X-ray absorption spectroscopic investigation [J].

Chen, Xing ;

Chu, Wangsheng ;

Wang, Lei ;

Wu, Ziyu .

JOURNAL OF MOLECULAR STRUCTURE, 2009, 920 (1-3) :40-44

[10] Theoretical modeling of water exchange on [Pd(H2O)(4)](2+), [Pt(H2O)(4)](2+), and trans-[PtCl2(H2O)(2)] [J].

Deeth, RJ ;

Elding, LI .

INORGANIC CHEMISTRY, 1996, 35 (17) :5019-5026

← 1 2 3 →