Syntheses and Molecular Structure of Dinuclear Transition Metal Complexes Bridged by Dipyridylamine Derivative Ligands

Stable dinuclear transition metal complexes,[(η 6 ‐C 6 H 6 ) 2 Ru 2 ( L1 )Cl 2 ] 2+ ( 1 ), [(η 6 ‐ p ‐ i PrC 6 H 4 Me) 2 Ru 2 ( L1 )Cl 2 ] 2+ ( 2 ), [(η 6 ‐C 6 Me 6 ) 2 Ru 2 ( L1 )Cl 2 ] 2+ ( 3 ), [(η 6 ‐C 6 H 6 ) 2 Ru 2 ( L2 )Cl 2 ] 2+ ( 4 ),[(η 6 ‐ p ‐ i PrC 6 H 4 Me) 2 Ru 2 ( L2 )Cl 2 ] 2+ ( 5 ), [(η 6 ‐C 6 Me 6 ) 2 Ru 2 ( L2 )Cl 2 ] 2+ ( 6 ), [(η 5 ‐C 5 Me 5 ) 2 Rh 2 ( L1 )Cl 2 ] 2+ ( 7 ), [(η 5 ‐C 5 Me 5 ) 2 Ir 2 ( L1 )Cl 2 ] 2+ ( 8 ),[(η 5 ‐C 5 Me 5 ) 2 Rh 2 ( L2 )Cl 2 ] 2+ ( 9 ), and [(η 5 ‐C 5 Me 5 ) 2 Rh 2 ( L2 )Cl 2 ] 2+ ( 10 ), with the bis‐bidentate ligands 1,3‐bis(di‐2‐pyridylaminomethyl)benzene ( L1 ) and 1,4‐bis(di‐2‐pyridylaminomethyl)benzene ( L2 ), which contain two chelating dipyridylamine units connected by an aromatic spacer, were synthesized. The cationic dinuclear complexes were isolated as their hexafluorophosphate salts and characterized by using a combination of NMR, IR, and UV/Vis spectroscopic methods and mass spectrometry. The solid‐state structure of complex 8 as a representative was determined by X‐ray structure analysis.