%0 Journal Article %A Lohrey, Trevor D. %A Maron, Laurent %A Bergman, Robert G. %A Arnold, John %D 2018 %T Heterotetrametallic Re–Zn–Zn–Re Complex Generated by an Anionic Rhenium(I) β‑Diketiminate %U https://acs.figshare.com/articles/journal_contribution/Heterotetrametallic_Re_Zn_Zn_Re_Complex_Generated_by_an_Anionic_Rhenium_I_Diketiminate/7556855 %R 10.1021/jacs.8b12494.s001 %2 https://ndownloader.figshare.com/files/14042819 %K Re %K zinc centers %K chemical oxidation %K Computational studies %K compound %K chemical reductant %K One-electron oxidation %K BDI %K ZnCl 2 %K Cp %K rhenium %K 1 yields %K dative interaction %X We report the synthesis of an anionic rhenium­(I) compound, Na­[Re­(η5-Cp)­(BDI)] (1; Cp = cyclopentadienide, BDI = N,N′-bis­(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) and initial investigations of its use as a strong chemical reductant and metalloligand. Chemical oxidation of 1 gives a rare example of a rhenium­(II) compound Re­(η5-Cp)­(BDI) (2), while protonation of 1 yields the rhenium­(III) hydride complex Re­(H)­(η5-Cp)­(BDI) (3). The reaction of 1 with ZnCl2 generated both 2 and the zinc­(I) compound [ZnRe­(η5-Cp)­(BDI)]2 (4), which features a linear, tetrametallic Re­(I)–Zn­(I)–Zn­(I)–Re­(I) core. Computational studies of 4 were performed to characterize the metal–metal bonding interactions; the results indicate a dative interaction from rhenium to zinc and covalent bonding between the two zinc centers. One-electron oxidation of 4 yielded both 2 and the triflate-bridged zinc­(II) complex [(μ-OTf)­ZnRe­(η5-Cp)­(BDI)]2 (5, OTf = trifluoromethanesulfonate). %I ACS Publications