Interconversion Between Cyclodimer and Cyclotrimer: Synthesis and Characterization of Cyclo-[Pd(II)Cl2(N-N)] Complexes
- Interconversion Between Cyclodimer and Cyclotrimer: Synthesis and Characterization of Cyclo-[Pd(II)Cl2(N-N)] Complexes
- 강현지; 노태환; 나영미; 유경호; 정옥상
- Cyclodimers; Cyclotrimers; Interconversion; Microspheres; Palladium(II) complexes
- Issue Date
- Inorganica chimica acta
- VOL 362, NO 6, 1963-1968
- The reaction of (COD)PdCl2 (COD = 1,5-cyclooctadiene) with (3-Py)2SiR1R2 (3-Py = 3-pyridyl; R1 = Ph,
R2 = Ph (m-pdps); R1 = Ph, R2=Me (m-pmps)) in acetone affords single crystals consisting of cyclodimers,
[PdCl2((3-Py)2SiR1R2)]2, whereas the same reaction in a mixture of dichloromethane and ethanol yields
amorphous spheres consisting of cyclotrimers, [PdCl2((3-Py)2SiR1R2)]3. In a boiling chloroform solution,
the cyclodimers are completely converted to cyclotrimers. These cyclotrimers, in the 10 60 C range,
are partly returned to cyclodimers. By contrast, the reaction of (COD)PdCl2 with (3-Py)2SiR1R2 (R1 = Bu,
R2= Me (m-pbms); R1 = dodecyl, R2=Me (m-pddms)) yields amorphous spheres consisting of cyclotrimers
irrespective of solvents. Both [PdCl2(m-pbms)]3 and [PdCl2(m-pddms)]3 are initially cyclotrimers
in chloroform, but they exist as a mixture of cyclodimers and cyclotrimers in solution in the 10 60 C
range. The metallacycles tend to form cyclodimers in the order m-pdps > m-pmps > m-pbms > m-pddms.
The equilibrium between cyclodimers and the cyclotrimers is sensitive to solvent, temperature, and concentration
as well as molecular structure.
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