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Xiufang Ma, Yanhua Lei and Zhaoxu Chen Theoretical Study on the Dissociation of Ligands in the Rhodium and Iridium Complexes Containing 1,1,1,5,5,5-Hexafluoroacetylacetonato Chinese Journal of Chemistry 31

Version of Record online: 28 JAN 2013 | DOI: 10.1002/cjoc.201201107

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Both ab initio and density functional methods have been uesed to explore the influence of central metals, conformation, solvent and protonation on the ligand dissociation of the (hfac-O,O)2M(L)(py) complexes (M=Rh(III) or Ir(III), hfac-O,O=k2-O,O-1,1,1, 5,5,5-hexafluoroacetylacetonato, L=CH3, CH3CO2, (CH3CO)2CH, CH3O or OH, py=pyridine). We demonstrate that ligand pyridine dissociates more easily than the "L" ligands under study in aprotic solvent and gas phase. The trans-conformation favors the dissociation of pyridine ligand significantly, compared with the cis-isomer. The benzene solvation only slightly stabilizes the complexes and does not change the ligand dissociation ordering. In particular, we show that pyridine is no longer the labile ligand in protic media. Instead, the oxygen-containing ligands (apart from those like hfac that form a cyclic structure) that coordinate to the central metal via oxygen atom become the labile ones.

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