We present a wide range of reactivity studies focused on the rhenium­(V) oxo imido complex (DippN)­(O)­Re­(BDI) (1, Dipp = 2,6-diisopropylphenyl and BDI = N,N′-bis­(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate). This complex, which was previously shown to possess a highly polarized Re oxo moiety, has proven to be a potent nucleophile and a valuable precursor to a variety of rare structural motifs in rhenium coordination complexes. For example, the Re oxo moiety of 1 undergoes [2 + 2] cycloadditions with carbodiimides, isocyanates, carbon dioxide, and isothiocyanates at room temperature. In the case of CO2, the cycloadduct with 1 (a carbonate complex) undergoes the facile ejection of CO2, demonstrating that this binding process is reversible. In the case of isothiocyanate, chalcogen metathesis with 1 takes place readily as the inclusion of a second equivalent of substrate in the reaction mixture rapidly yields a dithiocarbamate complex. This metathesis process was extended to the reactivity of 1 with phosphine chalcogenides, leading to the isolation of terminal sulfido imido and selenido imido complexes. Attempts to complete this series and generate the analogous terminal telluride led to the formation of a bidentate tritelluride (Te3 2–) complex. Triethylphosphine could only undergo oxygen atom transfer (OAT) with 1 under pressing thermal conditions that also led to C–N cleavage of the BDI ligand. In contrast, OAT between 1 and CO or 2,6-xylylisocyanide (XylNC) was found to be much more facile, proceeding within seconds at room temperature. While the addition of excess CO led to a rhenium­(III) imido dicarbonyl complex, we found that the addition of 2 equiv of XylNC was necessary to promote OAT, resulting in the isolation of a rare example of a stable metal isocyanate complex. Our experimental observations of CO and XylNC and their OAT reactions with 1 inspired a mechanistic computational study to probe the intermediates and kinetic barriers along these reaction pathways. Finally, we describe 1,2-additions of both protic and hydridic substrates with the Re oxo moiety of 1, which most notably led to the syntheses of an uncommon example of a terminal rhenium hydroxide complex and an oxo-bridged Re–O–Zr hetero-bi-metallic complex that was generated using Schwartz’s reagent (Cp2ZrHCl). A brief discussion of a potential alternative route to 1 is also presented.

We report the synthesis and reactivity studies of a pair of rhenium­(V) oxo imido complexes. Oxidation of the rhenium­(III) terminal oxo ORe­(η2-DHF)­(BDI) (DHF = dihydrofulvalene, BDI = N,N′-bis­(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) with organic azides R-N3 (R = t Bu, 2,6-diisopropylphenyl) yields the title complexes. Computational studies confirm that the rhenium oxo moieties of these complexes are polarized and correspondingly nucleophilic, owing to the preferential π bonding of the imido ligand to the Re center. This asymmetry in the metal–ligand multiple bond electronic structure facilitates the ready activation of B–C bonds in triarylboranes (BPh3 and B­(C6F5)3), yielding rhenium­(V) aryl borinate complexes. In the case of BPh3, subsequent cyclometalation of the 1,2-addition products was found to take place upon heating, ejecting benzene to form bidentate diphenylborinate complexes.