[3 + 2] Cycloadditions and Retrocycloadditions of Niobium Imido Complexes: An Experimental and Computational Mechanistic Study.

We demonstrate reactivity between a ß-diketiminate-supported niobium(III) imido complex and alkyl azides to form niobatetrazene complexes (BDI)Nb(NtBu)(RNNNNR) (BDI = N,N-bis(2,6-diisopropylphenyl)-3,5-dimethyl-ß-diketiminate; R = cyclohexyl (1), benzyl (2)). Intriguingly, niobatetrazene complexes 1 and 2 can be interconverted via addition of an appropriate alkyl azide, likely through a series of concerted [3 + 2] cycloaddition and retrocycloaddition reactions in which π-loaded bis(imido) intermediates are formed. The bis(imido) intermediates were trapped upon addition of alkyl isocyanides to yield five-coordinate bis(imido) complexes (BDI)Nb(NtBu)(NCy)(CNR) (R = tert-butyl (4a), cyclohexyl (4b)). Two computational methods─density functional theory and density functional tight binding (DFTB)─were employed to calculate the lowest energy pathway across the potential energy surface for this multistep transformation. Reaction path calculations for individual cycloaddition or retrocycloaddition processes along the multistep reaction pathway showed that these transformations occur via a concerted, yet highly asynchronous mechanism, in which the two bond-breaking or -making events do not occur simultaneously. The use of the DFTB method in this work highlights its advantages and utility for studying transition metal systems.

Diverse Reactivity of a Rhenium(V) Oxo Imido Complex: [2 + 2] Cycloadditions, Chalcogen Metathesis, Oxygen Atom Transfer, and Protic and Hydridic 1,2-Additions.

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-ß-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 (Te32-) 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.