Ring expansion and N,N-dimethylformamide-solvation of the cyclodimeric complex bis(3-pyridyl)dimethylsilanedicholoropalladium(II)

The reaction of (COD)PdCl₂ (COD = 1,5-cyclooctadiene) with (3-Py)₂SiMe₂ (bis(3-pyridyl)dimethylsilane) in acetone produces single crystals consisting of cyclodimers, [PdCl₂((3-Py)₂SiMe₂)]₂, whereas the similar reaction in a mixture of dichloromethane and ethanol yields amorphous submicrospheres consisting of cyclotrimers, [PdCl₂((3-Py)₂SiMe₂)]₃. In a boiling chloroform solution, the cyclodimers are completely converted to the cyclotrimers. The structures of both cyclic species are locked at temperatures below 0 °C. The cyclotrimer equilibrates to the cyclodimer, the cyclotrimer, and cyclotrimeric mono-DMF adduct, [Pd₃Cl₅(DMF)((3-Py)₂SiMe₂)₃]Cl in the mole ratio of 6:1:5 in DMF solution at room temperature. The cyclodimer finally reaches the equilibrium in the same condition. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.