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dc.contributor.authorBraband, Henrik
dc.contributor.authorBenz, Michael
dc.contributor.authorSpingler, Bernhard
dc.contributor.authorConradie, Jeanet
dc.contributor.authorRoger, Alberto
dc.contributor.authorGhosh, Abhik
dc.date.accessioned2022-02-25T13:23:59Z
dc.date.available2022-02-25T13:23:59Z
dc.date.issued2021-07-13
dc.description.abstractThe difference in [3 + 2] cycloaddition reactivity between fac- [MO<sub>3</sub>(tacn)]<sup>+</sup> (M = Re, <sup>99</sup>Tc; tacn = 1,4,7-triazacyclononane) complexes has been reexamined with a selection of unsaturated substrates including sodium 4- vinylbenzenesulfonate, norbornene, 2-butyne, and 2-methyl-3-butyn-2-ol (2MByOH). None of the substrates was found to react with the Re cation in water at room temperature, whereas the<sup> 99</sup>Tc reagent cleanly yielded the [3 + 2] cycloadducts. Interestingly, a bis-adduct was obtained as the sole product for 2MByOH, reflecting the high reactivity of a <sup>99</sup>TcO-enediolato monoadduct. On the basis of scalar relativistic and nonrelativistic density functional theory calculations of the reaction pathways, the dramatic difference in reactivity between the two metals has now been substantially attributed to differences in relativistic effects, which are much larger for the 5d metal. Furthermore, scalar-relativistic ΔG values were found to decrease along the series propene > norbornene > 2-butyne > dimethylketene, indicating major variations in the thermodynamic driving force as a function of the unsaturated substrate. The suggestion is made that scalar-relativistic effects, consisting of greater destabilization of the valence electrons of the 5d elements compared with those of the 4d elements, be viewed as a new design principle for novel <sup>99</sup>mTc/Re radiopharmaceuticals, as well as more generally in heavyelement coordination chemistry.en_US
dc.identifier.citationBraband H, Benz, Spingler, Conradie J, Roger, Ghosh A. Relativity as a Synthesis Design Principle: A Comparative Study of [3 + 2] Cycloaddition of Technetium(VII) and Rhenium(VII) Trioxo Complexes with Olefins. Inorganic Chemistry. 2021;60:11090-11097en_US
dc.identifier.cristinIDFRIDAID 1943978
dc.identifier.doi10.1021/acs.inorgchem.1c00995
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttps://hdl.handle.net/10037/24151
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalInorganic Chemistry
dc.relation.urihttps://doi.org/10.1021/acs.inorgchem.1c00995
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2021 The Author(s)en_US
dc.titleRelativity as a Synthesis Design Principle: A Comparative Study of [3 + 2] Cycloaddition of Technetium(VII) and Rhenium(VII) Trioxo Complexes with Olefinsen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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