ja8b12494_si_002.cif (1.22 MB)
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(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).
