Bi2Pt(hP9) by Low-Temperature Reduction of Bi13Pt3I7: Reinvestigation of the Crystal Structure and Chemical Bonding Analysis
作者： Martin Kaiser , Alexey I. Baranov , Michael Ruck
关键词: Octahedron 、 Crystal structure 、 Crystallography 、 Delocalized electron 、 Chemistry 、 Bond strength 、 Chemical bond 、 Stacking 、 Bismuth 、 Covalent bond
摘要: Bi2Pt(hP9) or γ-Bi2Pt is a high-temperature modification, which metastable below 420 °C. We obtained by reducing the layered bismuth subiodide Bi13Pt3I7 with high excess of n-butyllithium at 70 The crystals endure heterogeneous reaction and enormous mass loss. X-ray diffraction on small single-crystal revealed that crystallizes in acentric trigonal space group P31m (no. 157) = 657.30(7) pm c 616.65(7) pm. Although structure stacking layers edge-sharing [PtBi6/3] octahedra resemble 1H-polytype CdI2, Pt–Pt bonding interactions cause distortions introduce polarity to structure. Quantum chemical calculations followed real-space analysis reveal polar covalent between platinum atoms not limited nearest neighbor but essentially delocalized. bond strength much weaker than element.
mpg.de
sci-hub.se 参考文章(21)
R.F.W. Bader, M.E. Stephens, Fluctuation and correlation of electrons in molecular systems Chemical Physics Letters. ,vol. 26, pp. 445- 449 ,(1974) , 10.1016/0009-2614(74)89069-X
P. Cucka, C. S. Barrett, The crystal structure of Bi and of solid solutions of Pb, Sn, Sb and Te in Bi Acta Crystallographica. ,vol. 15, pp. 865- 872 ,(1962) , 10.1107/S0365110X62002297
Alexey I. Baranov, Miroslav Kohout, Electron localization and delocalization indices for solids Journal of Computational Chemistry. ,vol. 32, pp. 2064- 2076 ,(2011) , 10.1002/JCC.21784
T. Biswas, K. Schubert, Strukturuntersuchungen in den mischungen PtTlPb und PtPbBi Journal of The Less Common Metals. ,vol. 19, pp. 223- 243 ,(1969) , 10.1016/0022-5088(69)90099-X
R. Ponec, Chemical bonding in solids. On the generalization of the concept of bond order and valence for infinite periodical structures Theoretical Chemistry Accounts. ,vol. 114, pp. 208- 212 ,(2005) , 10.1007/S00214-005-0662-Z
Martin Kaiser, Anna Isaeva, Richard Skrotzki, Ulrich Schwarz, Michael Ruck, Metastable Bi8Ni8S by Reductive Pseudomorphosis of Bi8Ni8SI2 Zeitschrift für anorganische und allgemeine Chemie. ,vol. 637, pp. 2026- 2032 ,(2011) , 10.1002/ZAAC.201100286
Martin Pley, Mathias�S. Wickleder, Monomers, Chains and Layers of [Pt2(SO4)4] Units in the Crystal Structures of the Platinum(III) Sulfates (NH4)2[Pt2(SO4)4(H2O)2], K4[Pt2(SO4)5] and Cs[Pt2(SO4)3(HSO4)] European Journal of Inorganic Chemistry. ,vol. 2005, pp. 529- 535 ,(2005) , 10.1002/EJIC.200400755
John P. Perdew, Yue Wang, Accurate and simple analytic representation of the electron-gas correlation energy Physical Review B. ,vol. 45, pp. 13244- 13249 ,(1992) , 10.1103/PHYSREVB.45.13244
Xavier Fradera, Maggie A. Austen, Richard F. W. Bader, The Lewis Model and Beyond Journal of Physical Chemistry A. ,vol. 103, pp. 304- 314 ,(1999) , 10.1021/JP983362Q
H Okamoto, The Bi-Pt (Bismuth-Platinum) system Journal of Phase Equilibria. ,vol. 12, pp. 207- 210 ,(1991) , 10.1007/BF02645718