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Electron Counts for Face‐Bridged Octahedral Transition Metal Clusters
Author(s) -
Fan PengDong,
Deglmann Peter,
Ahlrichs Reinhart
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020301)8:5<1059::aid-chem1059>3.0.co;2-v
Subject(s) - octahedron , valence electron , electron counting , electron , cluster (spacecraft) , crystallography , transition metal , chemistry , valence (chemistry) , metal , open shell , acceptor , crystal structure , physics , condensed matter physics , catalysis , biochemistry , organic chemistry , quantum mechanics , computer science , programming language
Kohn–Sham orbital energy patterns were used to rationalize valence electron counts for stable face‐capped octahedral clusters [M 6 E 8 L 6 ] (E=S, Se, Te, Cl; L=CO, PMe 3 , Cl − ). When L is a π acceptor such as CO or PMe 3 , stable closed‐shell clusters are found for 80, 84, and 98 electrons. For L=Cl − (i.e. a π‐electron donor), only a count of 84 electrons appears favorable, as is found in [Mo 6 Cl 14 ] 2− . These counting rules apply to fivefold coordination of M, which becomes unstable if the electron count exceeds 98, for example, for M=Ni. In this case structures with tetrahedrally coordinated M are energetically favored, and this leads to different cluster structures.