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While alkylperoxomanganese(iii) (MnIII–OOR) intermediates are proposed in the catalytic cycles of several manganese-dependent enzymes, their characterization has proven to be a challenge due to their inherent thermal instability. Fundamental understanding of the structural and electronic properties of these important intermediates is limited to a series of complexes with thiolate-containing N4S− ligands. These well-characterized complexes are metastable yet unreactive in the direct oxidation of organic substrates. Because the stability and reactivity of MnIII –OOR complexes are likely to be highly dependent on their local coordination environment, we have generated two new MnIII–OOR complexes using a new amide-containing N5− ligand. Using the 2-(bis((6-methylpyridin-2-yl)methyl)amino)- N-(quinolin-8-yl)acetamide (H6Medpaq) ligand, we generated the [MnIII(OO)tBu)(6Medpaq)]OTf and [MnIII(OOCm)(6Medpaq)]OTf complexes through reaction of their MnII or MnIII precursors with t BuOOH and CmOOH, respectively. Both of the new Mn III–OOR complexes are stable at room-temperature (t1/2 = 5 and 8 days, respectively, at 298 K in CH3CN) and capable of reacting directly with phosphine substrates. The stability of these MnIII–OOR adducts render them amenable for detailed characterization, including by X-ray crystallography for [MnIII (OOCm)(6Medpaq)]OTf. Thermal decomposition studies support a decay pathway of the MnIII–OOR complexes by O–O bond homolysis. In contrast, direct reaction of [MnIII(OOCm)(6Medpaq)] + with PPh3 providedmore »evidence of heterolytic cleavage of the O–O bond. These studies reveal that both the stability and chemical reactivity of MnIII–OOR complexes can be tuned by the local coordination sphere.« less

Manganese ([Mn(CO) 3 ]) and rhenium tricarbonyl ([Re(CO) 3 ]) complexes represent a workhorse family of compounds with applications in a variety of fields. Here, the coordination, structural, and electrochemical properties of a family of mono- and bimetallic [Mn(CO) 3 ] and [Re(CO) 3 ] complexes are explored. In particular, a novel heterobimetallic complex featuring both [Mn(CO) 3 ] and [Re(CO) 3 ] units supported by 2,2′-bipyrimidine (bpm) has been synthesized, structurally characterized, and compared to the analogous monomeric and homobimetallic complexes. To enable a comprehensive structural analysis for the series of complexes, we have carried out new single crystal X-ray diffraction studies of seven compounds: Re(CO) 3 Cl(bpm), anti -[{Re(CO 3 )Cl} 2 (bpm)], Mn(CO) 3 Br(bpz) (bpz = 2,2′-bipyrazine), Mn(CO) 3 Br(bpm), syn - and anti -[{Mn(CO 3 )Br} 2 (bpm)], and syn -[Mn(CO 3 )Br(bpm)Re(CO) 3 Br]. Electrochemical studies reveal that the bimetallic complexes are reduced at much more positive potentials (Δ E ≥ 380 mV) compared to their monometallic analogues. This redox behavior is consistent with introduction of the second tricarbonyl unit which inductively withdraws electron density from the bridging, redox-active bpm ligand, resulting in more positive reduction potentials. [Re(CO 3 )Cl] 2 (bpm) was reducedmore »with cobaltocene; the electron paramagnetic resonance spectrum of the product exhibits an isotropic signal (near g = 2) characteristic of a ligand-centered bpm radical. Our findings highlight the facile synthesis as well as the structural characteristics and unique electrochemical behavior of this family of complexes.« less

Structurally elusive inositol hexakisphosphates have been trapped in host–guest sandwiches between two picolinamide macrocycles that remain intact in solution, aided by hydrogen bonds and electrostatic interactions. This first report of macrocyclic complexes of inositol hexakisphosphates provides structural insight to significant biosources of phosphorus that impact the global phosphorus cycle.

We exploit orthogonal chemical reactivity to generate uniformly multifunctionalized confined spaces. A metal–organic framework (MOF) material that has azide and hydroxyl reactive groups in well-defined locations is independently functionalized to yield a uniformly bifunctionalized material via multiple paths, including via a simultaneous, one-pot reaction.

Ligands based upon the 4,5‐diazafluorene core are an important class of emerging ligands in organometallic chemistry, but the structure and electronic properties of these ligands have received less attention than they deserve. Here, we show that 9,9′‐dimethyl‐4,5‐diazafluorene (Me₂daf) can stabilize low‐valent complexes through charge delocalization into its conjugated π‐system. Using a new platform of [Cp*Rh] complexes with three accessible formal oxidation states (+III, +II, and +I), we show that the methylation in Me₂daf is protective, blocking Brønsted acid‐base chemistry commonly encountered with other daf‐based ligands. Electronic absorption spectroscopy and single‐crystal X‐ray diffraction analysis of a family of eleven new compounds, including the unusual Cp*Rh(Me₂daf), reveal features consistent with charge delocalization driven by π‐backbonding into the LUMO of Me₂daf, reminiscent of behavior displayed by the workhorse 2,2′‐bipyridyl ligand. Taken together with spectrochemical data demonstrating clean conversion between oxidation states, our findings show that 9,9′‐dialkylated daf‐type ligands are promising building blocks for applications in reductive chemistry and catalysis.