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Diastereomerically Pure Heterodi‐ and Heterotetrametallic (Pd and Pt) Compounds: A Study of the Effect Induced by the Binding Mode of a Ferrocene‐Containing Ligand on Their Electrochemical Properties
Author(s) -
Talancón Daniel,
López Concepción,
FontBardía Mercè,
Calvet Teresa,
Roubeau Olivier
Publication year - 2014
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.201301274
Subject(s) - chemistry , ferrocene , ligand (biochemistry) , electrochemistry , medicinal chemistry , diastereomer , palladium , imine , stereochemistry , chirality (physics) , catalysis , organic chemistry , receptor , electrode , biochemistry , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics , quark
Abstract The reaction of (1 S ,2 R )‐[(η 5 ‐C 5 H 5 )Fe{(η 5 ‐C 5 H 4 )‐CH=N‐CH(Me)‐CH(OH)(C 6 H 5 )}] ( 1 ) with Na 2 [PdCl 4 ] in the presence of Na(OAc) · 3H 2 O produced three diastereomerically pure tetrametallic cyclopalladated complexes ( 6b I – 6b III ). In two of them ( 6b I and 6b II ), the imine 1 adopts the [C(sp 2 ,ferrocene),N] – mode of binding, but they differ in the planar chirality of the 1,2‐ferrocenyl unit ( S p in 6b I and R p in 6b II ), whereas ligand 1 in 6b III acts as a [C(sp 2 ,phenyl),N] – group. Treatment of 6b I – 6b III with PPh 3 gave [Pd{κ 2 ‐ C , N {(η 5 ‐C 5 H 3 )‐CH=N‐CH(Me)‐CH(OH)(C 6 H 5 )}Fe(η 5 ‐C 5 H 5 )}Cl(PPh 3 )] ( 7b I , 7b II ) and [Pd{κ 2 ‐ C , N {(C 6 H 4 )‐CH(OH)‐CH(Me)‐N=CH‐(η 5 ‐C 5 H 4 )}Fe(η 5 ‐C 5 H 5 )}Cl(PPh 3 )] ( 7b III ). The Pt II compounds [Pt{κ 2 ‐ C , N {(η 5 ‐C 5 H 3 )‐CH=NCH(Me)CH(OH)(C 6 H 5 )}Fe(η 5 ‐C 5 H 5 )}Cl(PPh 3 )] [( S p ,1 S ,2 R ) and ( R p ,1 S ,2 R ) diastereomers, 7a I and 7a II , respectively)] have also been prepared. The results of electrochemical studies of 6b I – 6b III , 7b I – 7b III , 7a I , 7a II and related Pt II complexes with 1 acting as an (N) or (N,O) – ligand are also reported. Comparison of the results provides conclusive evidence for the relative influence of the mode of binding of the ligand, the nature of the M II atom, the type of metallated atom C(sp 2 ,phenyl or ferrocenyl), the ancillary ligands and their relative disposition on the electrochemical properties of this type of compound.