Comparative study of [RuClCp(HdmoPTA-κP)(PPh3)][CF3SO3] and the heterobimetallic complexes [RuClCp(PPh3)-μ-dmoPTA-1κP:2κ2N,N′-M(acac-κ2O,O′)2] (M = Co, Ni, Zn; dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane)

Abstract

The synthesis of novel heterobimetallic derivatives of general formula [RuClCp(PPh₃)-μ-dmoPTA-1κP:2κ²N,N′-M(acac-κ²O,O′)₂] (M = Ni (3), Zn (4); dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) is described. The preparations of the ruthenium–cobalt analogue (M = Co (2)) and the starting compound [RuClCp(HdmoPTA-κP)(PPh₃)](CF₃SO₃) have been revised and their yield improved. Similar to 2, the solid state structures of 3 and 4 show that the dmoPTA-P and the dmoPTA-N_CH3 atoms are involved in the coordination to the {RuCpCl(PPh₃)} and {M(acac)₂} moieties, respectively. The size of the diffusing units is almost the same for the three binuclear complexes, indicating that they exhibit similar solution structures. The diamagnetic ruthenium–zinc derivative was fully characterized in solution at 193 K by NMR as two diastereomeric pairs of enantiomers (R-Ru, Δ-Zn; R-Ru, Λ-Zn; S-Ru, Δ-Zn; S-Ru, Λ-Zn). Finally, the electrochemical properties of the complexes have been investigated by cyclic voltammetry.