Reactivity of [Ge9{Si(SiMe3)3}3]−Towards Transition-Metal M2+Cations: Coordination and Redox Chemistry
| Autor: | Andreas Schnepf, Claudio Schrenk, Oleksandr Kysliak |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
010405 organic chemistry
Chemistry Organic Chemistry Inorganic chemistry chemistry.chemical_element General Chemistry 010402 general chemistry Metathesis 01 natural sciences Redox Catalysis 0104 chemical sciences law.invention Nickel Crystallography Transition metal law Cluster (physics) Reactivity (chemistry) Electron paramagnetic resonance Open shell |
| Zdroj: | Chemistry - A European Journal. 22:18787-18793 |
| ISSN: | 0947-6539 |
| DOI: | 10.1002/chem.201603441 |
| Popis: | Recently the metalloid cluster compound [Ge9 Hyp3 ]- (1; Hyp=Si(SiMe3 )3 ) was oxidatively coupled by an iron(II) salt to give the largest metalloid Group 14 cluster [Ge18 Hyp6 ]. Such redox chemistry is also possible with different transition metal (TM) salts TM2+ (TM=Fe, Co, Ni) to give the TM+ complexes [Fe(dppe)2 ][Ge9 Hyp3 ] (3; dppe=1,2-bis(diphenylphosphino)ethane), [Co(dppe)2 ][Ge9 Hyp3 ] (4), [Ni(dppe)(Ge9 Hyp3 )] (5) and [Ni(dppe)2 (Ge9 Hyp3 )]+ (6). Such a redox reaction does not proceed for Mn, for which a salt metathesis gives the first open shell [Hyp3 Ge9 -M-Ge9 Hyp3 ] cluster (2; M=Mn). The bonding of the transition metal atom to 1 is also possible for Ni (e.g., compound 6), in which one or even two nickel atoms can bind to 1. In contrast to this in case of the Fe and Co compounds 3 and 4, respectively, the transition-metal atom is not bound to the Ge9 core of 1. The synthesis and the experimentally determined structures of 2-6 are presented. Additionally the bonding within 2-6 is analyzed and discussed with the aid of EPR measurements and quantum chemical calculations. |
| Databáze: | OpenAIRE |
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