Abstract
Oxido and imido complexes of type ReOCl3(dppz) and Re(NPh)Cl3(dppz) having meridional geometry (where dppz is 3,6-di(2-pyridyl)pyridazine) have been isolated and characterized. The oxygen atom transfer from ReOCl3(dppz) to PPh3 has afforded Re(OPPh3)Cl3(dppz) which on chemical oxidation by HNO3 yielded [Re(OPPh3)Cl3(dppz)]ReO4. Treatment of Re(OPPh3)Cl3(dppz) with PPh3 has furnished facial Re(PPh3)Cl3(dppz). The second-order rate law and large negative entropy of activation (-15.8 eu) of the oxygen atom transfer reaction of ReOCl3(dppz) with PPh3 is consistent with an associative pathway initiating through nucleophilic phosphine attack to ReO * orbitals.
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