A General Pathway to Heterobimetallic Triple‐Decker Complexes

A General Pathway to Heterobimetallic Triple‐Decker Complexes

A systematic study on the reactivity of the triple‐decker complex [(Cp’’’Co)2(μ,η4:η4‐C7H8)] (A) (Cp’’’=1,2,4‐tritertbutyl‐cyclopentadienyl) towards sandwich complexes containing cyclo‐P3, cyclo‐P4, and cyclo‐P5 ligands under mild conditions is presented. The heterobimetallic triple‐decker sandwich...

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Bibliographic Details
Published in:Chemistry : a European journal 2020-02, Vol.26 (7), p.1518-1524
Main Authors: Piesch, Martin, Dielmann, Fabian, Reichl, Stephan, Scheer, Manfred
Format: Article
Language:eng
Subjects:
Chemical analysis
Chemistry
Cobalt
Communication
Communications
Crystal structure
cyclo-Pn ligands
Iron
Magnetic resonance spectroscopy
Mass spectrometry
Mass spectroscopy
nickel
NMR
NMR spectroscopy
Nuclear magnetic resonance
Spectroscopic analysis
Spectroscopy
Structural analysis
triple-decker complexes
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Summary:A systematic study on the reactivity of the triple‐decker complex [(Cp’’’Co)2(μ,η4:η4‐C7H8)] (A) (Cp’’’=1,2,4‐tritertbutyl‐cyclopentadienyl) towards sandwich complexes containing cyclo‐P3, cyclo‐P4, and cyclo‐P5 ligands under mild conditions is presented. The heterobimetallic triple‐decker sandwich complexes [(Cp*Fe)(Cp’’’Co)(μ,η5:η4‐P5)] (1) and [(Cp’’’Co)(Cp’’’Ni)(μ,η3:η3‐P3)] (3) (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) were synthesized and fully characterized. In solution, these complexes exhibit a unique fluxional behavior, which was investigated by variable temperature NMR spectroscopy. The dynamic processes can be blocked by coordination to {W(CO)5} fragments, leading to the complexes [(Cp*Fe)(Cp’’’Co)(μ3,η5:η4:η1‐P5){W(CO)5}] (2 a), [(Cp*Fe)(Cp’’’Co)(μ4,η5:η4:η1:η1‐P5){(W(CO)5)2}] (2 b), and [(Cp’’’Co)(Cp’’’Ni)(μ3,η3:η2:η1‐P3){W(CO)5}] (4), respectively. The thermolysis of 3 leads to the tetrahedrane complex [(Cp’’’Ni)2(μ,η2:η2‐P2)] (5). All compounds were fully characterized using single‐crystal X‐ray structure analysis, NMR spectroscopy, mass spectrometry, and elemental analysis. From double to triple: A synthetic route to otherwise inaccessible heterometallic triple‐decker complexes is reported (see scheme). The cobalt complex [(Cp’’’Co)2(toluene)] (Cp’’’=1,2,4‐tritertbutyl‐cyclopentadienyl) as a source for unsaturated {Cp’’’Co} fragments was reacted with the sandwich complexes [Cp*Fe(η5‐P5)], [Cp’’’Co((η4‐P4)] and [Cp’’’Ni(η3‐P3)] to form novel heterobimetallic triple‐decker complexes.
ISSN:0947-6539
1521-3765