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Biomedically relevant coordination chemistry of rhenium and the lanthanides Xu, Liang

Abstract

[ReO(ppme)X] (where ppme²⁻ is 2,5-diazo-N,N'-dimethylhexyl-l,6- bis(phenylphosphinate), X = Br₀․₃Cl₀․₇) has been synthesized via a substitution reaction and structurally characterized. [ReO(ppme)Cl] has been prepared by a reduction/complexation reaction from [NH₄][ReO₄]. [ReO(ppme)Cl] reacts with thiocyanate and benzene thiolate forming [ReO(ppme)X] (X = ⁻NCS, ⁻SC₆H₅), but the one-pot synthesis of the respective ternary thiolate complexes from perrhenate was not successful. The reduction/complexation reaction of p-methoxybenzenethiol, H₄ppmeCl₄, and perrhenate resulted in the formation of [H₃ppme][ReO(SR)₄], the reaction of which with ReO(ppme)Cl does not lead to [ReO(ppme)SR] in high yields. The oxorhenium(V) complexes with Hapmen (N,N'-bis(2- pyridylmethyl)ethylenediamine, an N₄ ligand) and H₂bped (N,N'-bis(2- pyridylmethyl)ethylenediamine-N,N'-diacetic acid, an N₄O₂ ligand) have been synthesized and structurally characterized. Along with [ReO(bbpen)]⁺ (where H₂bbpen is N,N'-bis(2- hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine, an N₄O₂ ligand) and [ReO(qtp)(OCH₃)₂]⁺ (where qtp, 2,2'-6',2"-6",2,"-quaterpyridine, has an N₄ donor set), [ReO(H₂pmen)Cl₂]+ and [ReO(bped)]⁺ complexes share a rare seven-coordinate structure with a distorted pentagonal bipyramidal geometry, which represents a potentially general structural motif in Re[sup v]=0 complexes. The complexes retained their structure in solution. [The rest of the abstract can be found in attached PDF file]

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