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Asymmetrically Difunctionalized 1,1′‐Ferrocenyl Metalloligands and Their Transition Metal Complexes
Author(s) -
Wagner Hanna E.,
Frank Nils,
Barani Elham,
Anson Christopher E.,
Bayer Lea,
Powell Annie K.,
Fink Karin,
Breher Frank
Publication year - 2022
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202100898
Subject(s) - chemistry , ferrocene , cyclopentadienyl complex , cyclic voltammetry , aryl , ring (chemistry) , electrochemistry , transition metal , ether , bipyridine , medicinal chemistry , nickel , reductive elimination , stereochemistry , polymer chemistry , crystallography , crystal structure , organic chemistry , catalysis , electrode , alkyl
The synthesis and full characterization of novel 1,1′‐difunctionalized ferrocene metalloligands is described. While one cyclopentadienyl ring has been functionalized with 2,2′‐bipyridine for secondary coordination, the second Cp ring has been decorated with different aryl moieties containing electron withdrawing groups such as 4‐(CF 3 )C 6 H 4 ( 2A ) 3,5‐(CF 3 ) 2 C 6 H 3 ( 2B ) or 4‐(NO 2 )C 6 H 4 ( 2C ). The newly developed metalloligands were reacted with [Pd(cod)Cl 2 ] ( 3A – C ), CuCl 2 ( 4A – C ) and trans ‐[(PPh 3 ) 2 Ni(Mes)Br] ( 5A , B ) to obtain the corresponding square‐planar and dimeric square‐pyramidal complexes. The electrochemical behaviour of the ligands and complexes was investigated with the aid of cyclic voltammetry and compared with the corresponding monofunctionalized derivatives. The influence of the implemented functional groups on the nickel complexes was then confirmed for the reductive elimination reaction of an aryl ether induced by oxidation of the corresponding methoxides ( 6A , B , D ). The experimental findings are supported by quantum chemical calculations.