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A General Pathway to Heterobimetallic Triple‐Decker Complexes
Author(s) -
Piesch Martin,
Dielmann Fabian,
Reichl Stephan,
Scheer Manfred
Publication year - 2020
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/chem.201905240
Subject(s) - cyclopentadienyl complex , chemistry , reactivity (psychology) , nuclear magnetic resonance spectroscopy , crystallography , thermal decomposition , crystal structure , spectroscopy , stereochemistry , catalysis , organic chemistry , medicine , physics , alternative medicine , pathology , quantum mechanics
A systematic study on the reactivity of the triple‐decker complex [(Cp’’’Co) 2 (μ,η 4 :η 4 ‐C 7 H 8 )] ( A ) (Cp’’’=1,2,4‐tritertbutyl‐cyclopentadienyl) towards sandwich complexes containing cyclo ‐P 3 , cyclo ‐P 4 , and cyclo ‐P 5 ligands under mild conditions is presented. The heterobimetallic triple‐decker sandwich complexes [(Cp*Fe)(Cp’’’Co)(μ,η 5 :η 4 ‐P 5 )] ( 1 ) and [(Cp’’’Co)(Cp’’’Ni)(μ,η 3 :η 3 ‐P 3 )] ( 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)(μ 3 ,η 5 :η 4 :η 1 ‐P 5 ){W(CO) 5 }] ( 2 a ), [(Cp*Fe)(Cp’’’Co)(μ 4 ,η 5 :η 4 :η 1 :η 1 ‐P 5 ){(W(CO) 5 ) 2 }] ( 2 b ), and [(Cp’’’Co)(Cp’’’Ni)(μ 3 ,η 3 :η 2 :η 1 ‐P 3 ){W(CO) 5 }] ( 4 ), respectively. The thermolysis of 3 leads to the tetrahedrane complex [(Cp’’’Ni) 2 (μ,η 2 :η 2 ‐P 2 )] ( 5 ). All compounds were fully characterized using single‐crystal X‐ray structure analysis, NMR spectroscopy, mass spectrometry, and elemental analysis.