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Synthesis and Reactivity of Bis(silylene)‐Coordinated Calcium and Divalent Lanthanide Complexes
Author(s) -
Sun Xiaofei,
Simler Thomas,
Reiter Kevin,
Weigend Florian,
Roesky Peter W.
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.202003417
Subject(s) - silylene , chemistry , divalent , ligand (biochemistry) , reactivity (psychology) , thermal decomposition , thermal stability , lanthanide , pyridine , chelation , photochemistry , stereochemistry , crystallography , inorganic chemistry , medicinal chemistry , organic chemistry , medicine , ion , biochemistry , receptor , alternative medicine , pathology , silicon
Divalent lanthanide complexes of Eu ( 1 ) and Yb ( 2 ) coordinated by a chelating pyridine‐based bis(silylene) ligand were isolated and fully characterized. Compared to the Eu II complex 1 , the Yb II complex 2 presents a lower thermal stability, resulting in the activation of one Si II −N bond and formation of an Yb III complex ( 3 ), which features a unique silylene‐pyridyl‐amido ligand. The different thermal stability of 1 and 2 points towards reduction‐induced cleavage of one Si II −N bond of the bis(silylene) ligand. Successful isolation of the corresponding redox‐inert bis(silylene) Ca II complex ( 5 ) was achieved at low temperature and thermal decomposition into a Ca II complex ( 4 ) bearing the same silylene‐pyridyl‐amido ligand was identified. In this case, the thermolysis reaction proceeds through another, non‐redox induced, mechanism. An alternative higher yielding route to 4 was developed through an in situ generated silylene‐pyridyl‐amine proligand.