Oxygen atom transfer from RevO to tertiary diphosphines: spacer length and chemical differentiation of products

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Abstract
The reaction of mer-[ReL(O)Cl3], [L = 2-(p-chlorophenylazo)-1-methylimidazole] with Ph2P(CH2)nPPh2 (abbreviated PnP) affords [ReL(OP1P)Cl3] 2a, [ReL(OP1PO)Cl3] 4 and [ReL(OP2P)Cl3] 2b, [Cl3LRe(OP2PO)ReLCl3] 5, all having mer geometry; unlike 2b which is stable in solution, 2a spontaneously isomerizes to fac-[ReL(P1PO)Cl3] via an associative pathway; the origin of the observed differentiation (2a vs. 2b and 4 vs. 5) is scrutinized in terms of structures and reaction models.