Substitution on Complexes of Oxo Metal Ions

The formation of the tungsten(VI) 0x0 diperoxo species in aqueous HCIO4 solution is governed by the rate law (67), where fc = 2.4 x 10 dm mol s at 298.2 It is thought that the reaction sequence occurs in steps (68)-(70). 

Ligand Substitution Processes in Dimeric and Higher Oligomeric Metal Complexes 

The dirhodium(II) tetrakis(/u-carboxyIate) complexes have been the subject of numerous studies as a consequence of their catalytic and antitumor activities, quite apart from their own intrinsic interest. The four bridging carboxylate ligands are inert to substitution, but the two axial ligands at either end of the dirhodium axis are labile. Thus it has been shown that the axial ligand substitution reactions of the diaqua dirhodium(II) tetracacetate species proceeds in the two steps shown in Eqs. (71) and (72), where the rate-determining formation of 

The use of soluble rhodium(II) carboxylate catalysts in the cyclopropanation of olefins is the origin of a very detailed crystallographic and spectrophotometric SF study of dirhodium(II) tris- and tetrakis(tritolylbenzoate), and tetrakis(pivalate)/ The Rh(II)-Rh(II) moiety at the Rh2(OsC)4 core resides inside a parallelepipedic box formed by the carboxylate ligands such that smaller ligands, such as pyridine, can coordinate at either end of the dirhodium axis. The formation 

Regioselective ligand exchange of in-plane acetate ligands on octakis(/t-acetato-0,0 )tetraplatinum(II) complex shown in Eq. (75) is characterized by the two-term rate law (76) where, in CDCI3 at 298.2 K, ko = 0.36 s and k = 4.4 dm mol s, as determined by a H NMR spin saturation transfer method, but no exchange is observed for the out-of-plane acetates. Molecular orbital 

---