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Cobalt Chalcogenide Clusters. Synthesis, Characterization and DFT Calculations of [Co 4 Se 2 (CO) 10 ] and [Co 4 Te 2 (CO) 11 ]. Crystal Structure of [Co 8 Se 4 (CO) 16 (μ‐dppa) 2 ]
Author(s) -
Sevillano Paloma,
Koenig Sven,
Himmel Daniel,
Fuhr Olaf,
Fenske Dieter
Publication year - 2005
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200570050
Subject(s) - chalcogen , cobalt , phosphine , chemistry , acetylene , chalcogenide , crystallography , metal , molecule , selenium , tellurium , metal carbonyl , cluster (spacecraft) , density functional theory , inorganic chemistry , computational chemistry , catalysis , organic chemistry , programming language , computer science
The reactions of [Co 2 (CO) 8 ] with E(SiMe 3 ) 2 (E = Se, Te) in CH 2 Cl 2 result in the formation of the compounds [Co 4 Se 2 (CO) 10 ]> ( 1 ) and [Co 4 Te 2 (CO) 11 ] ( 2 ), respectively. Both cluster complexes have similar molecular structures in which the cobalt atoms form four‐membered rings with μ 4 ‐bridging chalcogen atoms (Se and Te) above and below the plane of the metal atoms and the carbonyl ligands as either terminal or μ 2 ‐bridging ligands. DFT‐calculations for both compounds have been carried out in order to obtain some more information about their electronic distribution. In the presence of the phosphine Ph 2 PC≡CPPh 2 (dppa), the reaction of [Co 2 (CO) 8 ] with Se(SiMe 3 ) 2 leads to the formation of [Co 8 Se 4 (CO) 16 ( μ ‐dppa) 2 ] ( 3 ). During the reaction two molecules of [Co 2 (CO) 8 ] have been added to the acetylene groups of the dppa ligands, whilst the remaining cobalt atoms coordinate to the phosphorus atoms of the phosphine. In this compounds the selenium atoms act as μ 3 ‐ligands, bridging the metal atoms bonded to the phosphorus with those bonded to the acetylene groups.