Low-Temperature Nucleophilic Attack of Me₃SiO⁻and MeO⁻on Rhenium(I) and Rhenium(0) Carbonyl Complexes

Abstract

The reactivity of [Re(CO)5Cl] and [Re2(CO)10] with nucleophiles such as Me3SiO− and MeO− has been investigated by low-temperature NMR and by infrared spectroscopy particularly aimed at detecting the [Re(CO)5OR] species, which so far have eluded isolation, proposed as intermediates in the synthesis of the dimeric species [Re2(CO)6(μ-OR)3]− (R = SiMe3, Me). For both nucleophiles the first step involves an interaction with one specific carbonyl ligand and formation of new anionic complexes carrying a metal carboxy silyl or methyl ester, such as cis-[Re(CO)4(COOSiMe3)Cl]−, cis-[Re(CO)4(COOMe)Cl]−, [Re2(CO)9(COOSiMe3)]−, and [Re2(CO)9(COOMe)]−. The Re(I) complexes, stable only at low temperature, by further nucleophilic attack generate the well-known dimeric [Re2(CO)6(μ-OR)3]− complexes. The Re(0) metal carboxy-methyl esters derived from [Re2(CO)10] are thermally more stable and can be isolated in the solid state. In particular, the new complex [Re2(CO)9(COOMe)][NBu4] has been fully characterized by X-ray diffraction. In contrast, when the nucleophilic attack involves a weaker OR− nucleophile such as [(c-C6H11)7Si8O12O]− or a Re(I) pentacarbonyl substrate which bears a better leaving group such as the triflate, the low-temperature nucleophilic attack on a specific carbonyl ligand does not occur.

Guanidine-Functionalized Rhenium Cyclopentadienyl Carbonyl Complexes: Synthesis and Cooperative Activation of H–H and O–H Bonds

“…In addition to H 2 cleavage, we also examine the cooperative activation of the O–H bond of methanol, which reacts reversibly with the guanidine-appended complex to furnish a methoxycarbonyl complex protonated at the guanidine base; a detailed thermodynamic analysis of this transformation is also undertaken. Alkoxycarbonyl complexes are common in the middle to late transition metal series, , with a few structurally characterized examples from group 7 metals . To our knowledge, only one example exists of such a complex formed by intramolecular activation of methanol, and this lone example lacks any thermodynamic or kinetic analysis.…”