{μ‐PbSe}: A Heavy CO Homologue as an Unexpected Ligand |
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| Authors: | Dr Günther Thiele Yannick Franzke Priv‐Doz?Dr Florian Weigend Prof?Dr Stefanie Dehnen |
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| Affiliation: | 1. Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps‐Universit?t Marburg, Hans‐Meerwein‐Strasse 4, 35032 Marburg (Germany);2. Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT), Fritz‐Haber‐Weg 2, 76131 Karlsruhe (Germany);3. Institut für Nanotechnologie, Karlsruher Institut für Technologie, Hermann‐von‐Helmholtz Platz 1, 76344 Eggenstein‐Leopoldshafen (Germany) |
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| Abstract: | Reactions of K(18‐crown‐6)]2Pb2Se3] and K(2.2.2]crypt)]2Pb2Se3] with Rh(PPh3)3Cl] in en (ethane‐1,2‐diamine) afforded ionic compounds with Rh3(PPh3)6(μ3‐Se)2]? and Rh3(CN)2(PPh3)4(μ3‐Se)2(μ‐PbSe)]3? anions, respectively. The latter contains a PbSe ligand, a rather uncommon homologue of CO that acts as a μ‐bridge between two Rh atoms. Quantum chemical calculations yield a significantly higher bond energy for PbSe than for CO, since the size of the ligand orbitals better matches the comparably rigid Rh‐Se‐Rh angles and the resulting Rh???Rh distance. To rationalize the bent coordination of the ligand, orbitals with significant ligand contributions and their dependence on the bonding angle were investigated in detail. |
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| Keywords: | carbonyl homologues crystal structures DFT calculations lead rhodium clusters |
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