Complexes of the ReO³⁺/Re(CO)₃cores with multidentate N,O-Donor chelates

This study investigates the coordination modes of multidentate N,O-donor ligands toward the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The reactions of trans-[ReOX3(PPh3)2] (X = Cl, Br) with 4-aminoantipyrine (H2pap) were studied, and the complexes cis-[ReX2(pap)(H2pap)(PPh3)](ReO4) were isolated. The X-ray crystal structures show that both complexes display a distorted octahedral geometry around the central rhenium atom, and are mirror images of each other. The ligand pap is coordinated monodentately through the doubly deprotonated amino nitrogen as an imide, and H2pap acts as a neutral bidentate chelate, with coordination through the neutral amino nitrogen and the ketonic oxygen. The attempted synthesis of the potentially hexadentate Schiff base ligand 1,2-bis(2-{(Z)- [(2-hydroxyphenyl)imido]methyl}phenoxy)benzene from the condensation reaction of 2- (2-((2-aminophenoxy)methyl)benzyloxy)benzenamine and salicylaldehyde produced the zwitterion derivative (H2ono) of 2-{(Z)-[2-(hydroxyphenyl)imino]methyl}phenol. The tridentate Schiff bases (Z)-2-(2-aminobenzylideneamino)phenol (H3onn) and (Z)-2-(2- (methylthio)benzylideneamino)phenol (Hons) were prepared in a similar manner. The reaction of H2ono with trans-[ReOBr3(PPh3)2] surprisingly led to the isolation of the rhenium(III) complex [ReBr(PPh3)2(ono)], in which ono acts as a dianionic tridentate ligand. The reaction of H3onn with trans-[ReOBr3(PPh3)2] produced the imidorhenium(V) complex salt [ReBr(PPh3)2(onn)]Br, in which onn is coordinated as a trianionic tridentate imidoiminophenolate. The reaction of Hons with [Re(CO)5Br] led to the further decomposition of the Hons ligand, and the rhenium(I) product fac- [Re(CO)3(ons)(Hno)] (Hno = 2-aminophenol) was isolated, with ons coordinated as a monoanionic bidentate chelate (with a free SCH3 group), and Hno present as a neutral monodentate ligand with coordination through the amino nitrogen atom. Abstract Nelson Mandela Metropolitan University vi The reactions of the potentially hexadentate ligand N,N’-{ethane-1,2- diylbis[nitrilomethylidenebenzene-1,2-diyl]}bis(2-aminobenzeneimine) (H2ted) with rhenium(V) starting materials resulted in the decomposition of the H2ted molecule to give different coordinated multidentate ligands coordinated to the rhenium(V) centers. In the reaction of H2ted with trans-[ReOBr3(PPh3)2] in ethanol, the highly unusual ‘3+3’ complex cation [Re(tnn)(Htnn)]Br2 was isolated, in which tnn is coordinated as a tridentate imido-imino-amine, and Htnn is present as a tridentate monoanionic amidoimino- amine chelate (H2tnn = N-(2-aminophenylmethylidene)ethane-1,2-diamine). With trans-[ReO2(py)4]Cl as starting material, the neutral complex [ReO(dne)] was found, in which the tetradentate chelate dne acts as a triamido-imine. The reaction of cis- [ReO2I(PPh3)2] with H2ted led to the formation of the monocationic complex salt [ReO(ane)]PF6, with ane acting as a tetradentate dianionic diamidodiimine (H2ane = N,N’-bis[(2-aminophenyl)methylidene] ethane-1,2-diamine). The seven-coordinate rhenium(III) complex cation…