Ca(10)Pt(7)Tt(3) (Tt = Si, Ge): New Platinide Phases Featuring Electron-Rich 4c-6e Bonded [Pt(7)Tt(3)](20-) Intermetalloid Clusters.
(2012) In Inorganic Chemistry 51(21). p.11980-11985- Abstract
- Two new phases Ca(10)Pt(7)Tt(3) (with Tt = Si, Ge) were obtained by reacting stoichiometric mixtures of the elements at high temperature. Their structures were refined from single crystal X-ray diffraction data. They are isostructural and crystallize in the Ba(10)Al(3)Ge(7) type structure, space group P6(3)/mcm (No. 193) with a = b = 8.7735(3) Å, c = 13.8260(5) Å, V = 921.66(6) Å(3), Z = 2 for Tt = Si, and a = b = 8.7995(6) Å, c = 13.9217(14) Å, V = 933.56(16) Å(3) for Tt = Ge phase. The most interesting structural features in these phases are the propeller shape {Pt(7)Tt(3)} (Tt = Si, Ge) intermetalloid clusters in a D(3h) local symmetry. LMTO electronic structure calculations and COHP analyses reveal that both Ca(10)Pt(7)Tt(3) (Tt = Si,... (More)
- Two new phases Ca(10)Pt(7)Tt(3) (with Tt = Si, Ge) were obtained by reacting stoichiometric mixtures of the elements at high temperature. Their structures were refined from single crystal X-ray diffraction data. They are isostructural and crystallize in the Ba(10)Al(3)Ge(7) type structure, space group P6(3)/mcm (No. 193) with a = b = 8.7735(3) Å, c = 13.8260(5) Å, V = 921.66(6) Å(3), Z = 2 for Tt = Si, and a = b = 8.7995(6) Å, c = 13.9217(14) Å, V = 933.56(16) Å(3) for Tt = Ge phase. The most interesting structural features in these phases are the propeller shape {Pt(7)Tt(3)} (Tt = Si, Ge) intermetalloid clusters in a D(3h) local symmetry. LMTO electronic structure calculations and COHP analyses reveal that both Ca(10)Pt(7)Tt(3) (Tt = Si, Ge) phases are charge optimized, which is not predicted by the classical Zintl concept and the octet or Wade-Mingo's rules, but rather by a more complex bonding model based on the unprecedented electron-rich 4c-6e multicenter bonding. The clusters are best described as three-condensed trigonal planar [TtPt(3)](8-) units, resulting in a central Pt atom also with a trigonal planar coordination of three symmetrical equivalent Si/Ge atoms that are further connected to two terminal Pt atoms each. The "trefoil" electron-rich multicenter bonding is proposed here for the first time, and may be viewed as a unique bonding feature with potential relevance for the catalytic properties of the noble metal platinum. (Less)
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https://lup.lub.lu.se/record/3160483
- author
- Doverbratt, Isa LU ; Ponou, Simeon LU ; Lidin, Sven LU and Fredrickson, Daniel C
- organization
- publishing date
- 2012
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Inorganic Chemistry
- volume
- 51
- issue
- 21
- pages
- 11980 - 11985
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000313220200088
- pmid:23088157
- scopus:84868343897
- pmid:23088157
- ISSN
- 1520-510X
- DOI
- 10.1021/ic301867q
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Polymer and Materials Chemistry (LTH) (011001041)
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- a75bd8cd-16d5-4451-a830-a2e2f6ec8d92 (old id 3160483)
- date added to LUP
- 2016-04-01 10:30:33
- date last changed
- 2022-01-25 23:54:17
@article{a75bd8cd-16d5-4451-a830-a2e2f6ec8d92,
abstract = {{Two new phases Ca(10)Pt(7)Tt(3) (with Tt = Si, Ge) were obtained by reacting stoichiometric mixtures of the elements at high temperature. Their structures were refined from single crystal X-ray diffraction data. They are isostructural and crystallize in the Ba(10)Al(3)Ge(7) type structure, space group P6(3)/mcm (No. 193) with a = b = 8.7735(3) Å, c = 13.8260(5) Å, V = 921.66(6) Å(3), Z = 2 for Tt = Si, and a = b = 8.7995(6) Å, c = 13.9217(14) Å, V = 933.56(16) Å(3) for Tt = Ge phase. The most interesting structural features in these phases are the propeller shape {Pt(7)Tt(3)} (Tt = Si, Ge) intermetalloid clusters in a D(3h) local symmetry. LMTO electronic structure calculations and COHP analyses reveal that both Ca(10)Pt(7)Tt(3) (Tt = Si, Ge) phases are charge optimized, which is not predicted by the classical Zintl concept and the octet or Wade-Mingo's rules, but rather by a more complex bonding model based on the unprecedented electron-rich 4c-6e multicenter bonding. The clusters are best described as three-condensed trigonal planar [TtPt(3)](8-) units, resulting in a central Pt atom also with a trigonal planar coordination of three symmetrical equivalent Si/Ge atoms that are further connected to two terminal Pt atoms each. The "trefoil" electron-rich multicenter bonding is proposed here for the first time, and may be viewed as a unique bonding feature with potential relevance for the catalytic properties of the noble metal platinum.}},
author = {{Doverbratt, Isa and Ponou, Simeon and Lidin, Sven and Fredrickson, Daniel C}},
issn = {{1520-510X}},
language = {{eng}},
number = {{21}},
pages = {{11980--11985}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Inorganic Chemistry}},
title = {{Ca(10)Pt(7)Tt(3) (Tt = Si, Ge): New Platinide Phases Featuring Electron-Rich 4c-6e Bonded [Pt(7)Tt(3)](20-) Intermetalloid Clusters.}},
url = {{http://dx.doi.org/10.1021/ic301867q}},
doi = {{10.1021/ic301867q}},
volume = {{51}},
year = {{2012}},
}