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The bimolecular reaction of Re V OCl3(dppz), 1, (where dppz is 3,6-di(2-pyridyl) pyridazine) with excess diphosphine Ph2P(CH2)xPPh2 (x=1-4) has furnished Re III (OPPh2(CH2)x PPh2)Cl3(dppz), 2 with a dangling phosphine function which is spontaneously converted in solution to Re III (PPh2(CH2)xP(O)Ph2)Cl3(dppz), 3. The complex 2 (x=1) on reaction with excess 1 affords mononuclear Re III (OPPh2(CH2)P(O)Ph2)Cl3(dppz), 4 while for x= 2-4 binuclear complex (dppz)Cl3Re III (OPPh2(CH2)xPPh2O)Re III Cl3(dppz), 5 is obtained. Rate studies of the twin isomerization (linkage-cum-geometrical) reaction 23 revealed that the reaction is intramolecular in nature. It is initiated by the nucleophilic attack of the metal by the dangling phosphine function. The process slows down nearly exponentially as the diphosphine spacer length x increases. The oxidized complex (Re IV (OPPh2(CH2)PPh2)Cl3(dppz))ReO4, 6 does not isomerize.

chemical science transactions

Oxygen Atom Transfer from Pyridylpyridazine Chelated Oxidorhenium(V) Complex to Diphosphines: Twin Isomerization, Effects of Diphosphine Spacer Length and Metal Oxidation State