Heterotetrametallic Re–Zn–Zn–Re Complex Generated by an Anionic Rhenium(I) β‑Diketiminate
dataset
posted on 2018-12-20, 00:00 authored by Trevor
D. Lohrey, Laurent Maron, Robert G. Bergman, John ArnoldWe
report the synthesis of an anionic rhenium(I) compound, Na[Re(η<sup>5</sup>-Cp)(BDI)] (<b>1</b>; Cp = cyclopentadienide, BDI = <i>N</i>,<i>N</i>′-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 <b>1</b> gives a rare
example of a rhenium(II) compound Re(η<sup>5</sup>-Cp)(BDI)
(<b>2</b>), while protonation of <b>1</b> yields the rhenium(III)
hydride complex Re(H)(η<sup>5</sup>-Cp)(BDI) (<b>3</b>). The reaction of <b>1</b> with ZnCl<sub>2</sub> generated
both <b>2</b> and the zinc(I) compound [ZnRe(η<sup>5</sup>-Cp)(BDI)]<sub>2</sub> (<b>4</b>), which features a linear,
tetrametallic Re(I)–Zn(I)–Zn(I)–Re(I) core. Computational
studies of <b>4</b> 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 <b>4</b> yielded both <b>2</b> and the triflate-bridged zinc(II) complex [(μ-OTf)ZnRe(η<sup>5</sup>-Cp)(BDI)]<sub>2</sub> (<b>5</b>, OTf = trifluoromethanesulfonate).
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