Structural systematics of the {ReO}3+ core with ‘3+2’ ligand donor sets

The reactions of [ReOCl3(PPh3)2] with the appropriate tridentate and bidentate ligands provide a facile route for the synthesis of a diverse family of compounds of the {Re(V)O}3+ core with a ‘3+2’ ligand set. The structural prototype for the series is [ReO{OCH2CH2SCH2CH2O}{OCH2CH2SCH2CH2OH}] (1) which exhibits distorted octahedral geometry, defined by the two oxygen and sulfur donors of the tridentate ligand in a facial arrangement, the oxygen and sulfur donors of the bidentate ligand, and the oxo-donor. Compounds 2–5 are variants of the type [ReO(OCH2CH2SCH2CH2O)(S∧N)] where S∧N is a bidentate ligand of the mercaptopyridine or mercaptopyrimidine class. Similarly, compounds 6–17 are of the type [ReO(OCH2CH2NRCH2CH2O)(S∧N)] with the same bidentate ligands as for 2–5 and R=CH3, CH2CH3, CH2CH2CH2CH3, and C(CH3)3.