Trivalent Cations Slow Electron Transfer to Macrocyclic Heterobimetallic Complexes.

Incorporation of secondary redox-inactive cations into heterobimetallic complexes is an attractive strategy for modulation of metal-centered redox chemistry, but quantification of the consequences of incorporating strongly Lewis acidic trivalent cations has received little attention. Here, a family of seven heterobimetallic complexes that pair a redox-active nickel center with La3+, Y3+, Lu3+, Sr2+, Ca2+, K+, and Na+ (in the form of their triflate salts) have been prepared on a heteroditopic ligand platform to understand how chemical behavior varies across the comprehensive series. Structural data from X-ray diffraction analysis demonstrate that the positions adopted by the secondary cations in the crown-ether-like site of the ligand relative to nickel are dependent primarily on the secondary cations' ionic radii and that the triflate counteranions are bound to the cations in all cases. Electrochemical data, in concert with electron paramagnetic resonance studies, show that nickel(II)/nickel(I) redox is modulated by the secondary metals; the heterogeneous electron-transfer rate is diminished for the derivatives incorporating trivalent metals, an effect that is dependent on steric crowding about the nickel metal center and that was quantified here with a topographical free-volume analysis. As related analyses carried out here on previously reported systems bear out similar relationships, we conclude that the placement and identity of both the secondary metal cations and their associated counteranions can afford unique changes in the (electro)chemical behavior of heterobimetallic species.

Enhanced Understanding of Structure-Function Relationships for Oxomanganese(IV) Complexes.

A series of manganese(II) and oxomanganese(IV) complexes supported by neutral, pentadentate ligands with varied equatorial ligand-field strength (N3pyQ, N2py2I, and N4pyMe2) were synthesized and then characterized using structural and spectroscopic methods. On the basis of electronic absorption spectroscopy, the [MnIV(O)(N4pyMe2)]2+ complex has the weakest equatorial ligand field among a set of similar MnIV-oxo species. In contrast, [MnIV(O)(N2py2I)]2+ shows the strongest equatorial ligand-field strength for this same series. We examined the influence of these changes in electronic structure on the reactivity of the oxomanganese(IV) complexes using hydrocarbons and thioanisole as substrates. The [MnIV(O)(N3pyQ)]2+ complex, which contains one quinoline and three pyridine donors in the equatorial plane, ranks among the fastest MnIV-oxo complexes in C-H bond and thioanisole oxidation. While a weak equatorial ligand field has been associated with high reactivity, the [MnIV(O)(N4pyMe2)]2+ complex is only a modest oxidant. Buried volume plots suggest that steric factors dampen the reactivity of this complex. Trends in reactivity were examined using density functional theory (DFT)-computed bond dissociation free energies (BDFEs) of the MnIIIO-H and MnIV ═ O bonds. We observe an excellent correlation between MnIV═O BDFEs and rates of thioanisole oxidation, but more scatter is observed between hydrocarbon oxidation rates and the MnIIIO-H BDFEs.

Vanadyl as a Spectroscopic Probe of Tunable Ligand Donor Strength in Bimetallic Complexes.

Incorporation of secondary metal ions into heterobimetallic complexes has emerged as an attractive strategy for rational tuning of compounds' properties and reactivity, but direct solution-phase spectroscopic interrogation of tuning effects has received less attention than it deserves. Here, we report the assembly and study of a series of heterobimetallic complexes containing the vanadyl ion, [VO]2+, paired with monovalent cations (Cs+, Rb+, K+, Na+, and Li+) and a divalent cation (Ca2+). These complexes, which can be isolated in pure form or generated in situ from a common monometallic vanadyl-containing precursor, enable experimental spectroscopic and electrochemical quantification of the influence of the incorporated cations on the properties of the vanadyl moiety. The data reveal systematic shifts in the V-O stretching frequency, isotropic hyperfine coupling constant for the vanadium center, and V(V)/V(IV) reduction potential in the complexes. These shifts can be interpreted as charge density effects parametrized through the Lewis acidities of the cations, suggesting broad potential for the vanadyl ion to serve as a spectroscopic probe in multimetallic species.

Evidence for Uranium(VI/V) Redox Supported by 2,2'-Bipyridyl-6,6'-dicarboxylate.

The 2,2'-bipyridyl-6,6'-dicarboxylate ligand (bdc) has been shown in prior work to effectively capture the uranyl(VI) ion, UO22+, from aqueous solutions. However, the redox properties of the uranyl complex of this ligand have not been addressed despite the relevance of uranium-centered reduction to the nuclear fuel cycle and the presence of a bipyridyl core in bdc, a motif long recognized for its ability to support redox chemistry. Here, the bdc complex of UO22+ (1-UO2) has been synthetically prepared and isolated under nonaqueous conditions for the study of its reductive chemical and electrochemical behavior. Spectrochemical titration data collected using decamethylcobaltocene (Cp*2Co) as the reductant demonstrate that 1e- reduction of 1-UO2 is accessible, and companion near-infrared and infrared spectroscopic data, along with theoretical findings from density functional theory, provide evidence that supports the accessibility of the U(V) oxidation state. Data obtained for control ruthenium complexes of bdc and related polypyridyl dicarboxylate ligands provide a counterpoint to these findings; ligand-centered reduction of bdc in these control compounds occurs at potentials more negative than those measured for reduction of 1-UO2, further supporting the generation of uranium(V) in 1-UO2. Taken together, these results underscore the usefulness of bdc as a ligand for actinyl ions and suggest that it could be useful for further studies of the reductive activation of these unique species.

Evidence for Charge Delocalization in Diazafluorene Ligands Supporting Low-Valent [Cp*Rh] Complexes.

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 (Me2 daf) 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 Me2 daf 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(Me2 daf), reveal features consistent with charge delocalization driven by π-backbonding into the LUMO of Me2 daf, 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.

Revealing the Influence of Diverse Secondary Metal Cations on Redox-Active Palladium Complexes.

Incorporation of redox-inactive metals into redox-active complexes and catalysts attracts attention for engendering new reactivity modes, but this strategy has not been extensively investigated beyond the first-row of the transition metals. Here, the isolation and characterization of the first series of heterobimetallic complexes of palladium with mono-, di-, and tri-valent redox-inactive metal ions are reported. A Reinhoudt-type heteroditopic ligand with a salen-derived [N2 ,O2 ] binding site for Pd and a crown-ether-derived [O6 ] site has been used to prepare isolable adducts of the Lewis acidic redox-inactive metal ions (Mn+ ). Comprehensive data from single-crystal X-ray diffraction analysis reveal distinctive trends in the structural properties of the heterobimetallic species, including an uncommon dependence of the Pd⋅⋅⋅M distance on Lewis acidity. The reorganization energy associated with reduction of the heterobimetallic species is strongly modulated by Lewis acidity, with the slowest heterogeneous electron transfer kinetics associated with the strongest incorporated Lewis acids. This hitherto unexplored reorganization energy penalty for electron transfer contrasts with prior thermodynamic studies, revealing that kinetic parameters should be considered in studies of reactivity involving heterobimetallic species.

Remote Oxidative Activation of a [Cp*Rh] Monohydride.

Half-sandwich rhodium monohydrides are often proposed as intermediates in catalysis, but little is known regarding the redox-induced reactivity accessible to these species. Herein, the bis(diphenylphosphino)ferrocene (dppf) ligand has been used to explore the reactivity that can be induced when a [Cp*Rh] monohydride undergoes remote (dppf-centered) oxidation by 1e- . Chemical and electrochemical studies show that one-electron redox chemistry is accessible to Cp*Rh(dppf), including a unique quasi-reversible RhII/I process at -0.96 V vs. ferrocenium/ferrocene (Fc+/0 ). This redox manifold was confirmed by isolation of an uncommon RhII species, [Cp*Rh(dppf)]+ , that was characterized by electron paramagnetic resonance (EPR) spectroscopy. Protonation of Cp*Rh(dppf) with anilinium triflate yielded an isolable and inert monohydride, [Cp*Rh(dppf)H]+ , and this species was found to undergo a quasireversible electrochemical oxidation at +0.41 V vs. Fc+/0 that corresponds to iron-centered oxidation in the dppf backbone. Thermochemical analysis predicts that this dppf-centered oxidation drives a dramatic increase in acidity of the Rh-H moiety by 23 pKa units, a reactivity pattern confirmed by in situ 1 H NMR studies. Taken together, these results show that remote oxidation can effectively induce M-H activation and suggest that ligand-centered redox activity could be an attractive feature for the design of new systems relying on hydride intermediates.

Synthesis and Characterization of Bimetallic Nanoclusters Stabilized by Chiral and Achiral Polyvinylpyrrolidinones. Catalytic C(sp3)-H Oxidation.

Second-generation chiral-substituted poly-N-vinylpyrrolidinones (CSPVPs) (-)-1R and (+)-1S were synthesized by free-radical polymerization of (3aR,6aR)- and (3aS,6aS)-5-ethenyl-tetrahydro-2,2-dimethyl-4H-1,3-dioxolo[4,5-c]pyrrol-4-one, respectively, using thermal and photochemical reactions. They were produced from respective d-isoascorbic acid and d-ribose. In addition, chiral polymer (-)-2 was also synthesized from the polymerization of (S)-3-(methoxymethoxy)-1-vinylpyrrolidin-2-one. Molecular weights of these chiral polymers were measured using HRMS, and the polymer chain tacticity was studied using 13C NMR spectroscopy. Chiral polymers (-)-1R, (+)-1S, and (-)-2 along with poly-N-vinylpyrrolidinone (PVP, MW 40K) were separately used in the stabilization of Cu/Au or Pd/Au nanoclusters. CD spectra of the bimetallic nanoclusters stabilized by (-)-1R and (+)-1S showed close to mirror-imaged CD absorption bands at wavelengths 200-300 nm, revealing that bimetallic nanoclusters' chiroptical responses are derived from chiral polymer-encapsulated nanomaterials. Chemo-, regio-, and stereo-selectivity was found in the catalytic C-H group oxidation reactions of complex bioactive natural products, such as ambroxide, menthofuran, boldine, estrone, dehydroabietylamine, 9-allogibberic acid, and sclareolide, and substituted adamantane molecules, when catalyst Cu/Au (3:1) or Pd/Au (3:1) stabilized by CSPVPs or PVP and oxidant H2O2 or t-BuOOH were applied. Oxidation of (+)-boldine N-oxide 23 using NMO as an oxidant yielded 4,5-dehydroboldine 27, and oxidation of (-)-9-allogibberic acid yielded C6,15 lactone 47 and C6-ketone 48.

Controlling the Reactivity of a Metal-Hydroxo Adduct with a Hydrogen Bond.

The enzymes manganese lipoxygenase (MnLOX) and manganese superoxide dismutase (MnSOD) utilize mononuclear Mn centers to effect their catalytic reactions. In the oxidized MnIII state, the active site of each enzyme contains a hydroxo ligand, and X-ray crystal structures imply a hydrogen bond between this hydroxo ligand and a cis carboxylate ligand. While hydrogen bonding is a common feature of enzyme active sites, the importance of this particular hydroxo-carboxylate interaction is relatively unexplored. In this present study, we examined a pair of MnIII-hydroxo complexes that differ by a single functional group. One of these complexes, [MnIII(OH)(PaPy2N)]+, contains a naphthyridinyl moiety capable of forming an intramolecular hydrogen bond with the hydroxo ligand. The second complex, [MnIII(OH)(PaPy2Q)]+, contains a quinolinyl moiety that does not permit any intramolecular hydrogen bonding. Spectroscopic characterization of these complexes supports a common structure, but with perturbations to [MnIII(OH)(PaPy2N)]+, consistent with a hydrogen bond. Kinetic studies using a variety of substrates with activated O-H bonds, revealed that [MnIII(OH)(PaPy2N)]+ is far more reactive than [MnIII(OH)(PaPy2Q)]+, with rate enhancements of 15-100-fold. A detailed analysis of the thermodynamic contributions to these reactions using DFT computations reveals that the former complex is significantly more basic. This increased basicity counteracts the more negative reduction potential of this complex, leading to a stronger O-H BDFE in the [MnII(OH2)(PaPy2N)]+ product. Thus, the differences in reactivity between [MnIII(OH)(PaPy2Q)]+ and [MnIII(OH)(PaPy2N)]+ can be understood on the basis of thermodynamic considerations, which are strongly influenced by the ability of the latter complex to form an intramolecular hydrogen bond.

Incorporation of [Cp*Rh] and [Cp*Ir] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation.

The synthesis of multimetallic compounds can enable the placement of two or more metals in close proximity, but efforts in this area are often hindered by reagent incompatibilities and a lack of selectivity. Here, we show that organometallic half-sandwich [Cp*M] (M = Rh, Ir) fragments (where Cp* is η5-pentamethylcyclopentadienyl) can be cleanly installed into metallomacrocyclic structures based on the workhorse diimine-monooxime-monooximato ligand system. Six new heterobimetallic compounds have been prepared to explore this synthetic chemistry, which relies on in situ protonolysis reactivity with precursor Ni(II) or Co(III) monometallic complexes in the presence of suitable [Cp*M] species. Solid-state X-ray diffraction studies confirm installation of the [Cp*M] fragments into the metallomacrocycles via effective chelation of the Rh(III) and Ir(III) centers by the nascent dioximato site. Contrasting with square-planar Ni(II) centers, the Co(III) centers prefer octahedral geometry in the heterobimetallic compounds, promoting bridging ligation of acetate across the two metals. Spectroscopic and electrochemical studies reveal subtle influences of the metals on each other's properties, consistent with the moderate M'···M distances of ca. 3.6-3.7 Å in the modular compounds. Taken together, our results show that heterobimetallic complexes can be assembled with organometallic [Cp*M] fragments on the diimine-dioximato platform.

Hydrophilic and hydrophobic carboxamide pincers as anion hosts.

Hydrophobic and hydrophilic, monotopic and ditopic carboxamide pincer hosts containing ethyl, hexyl, 2-hydroxyethyl and 2-hydroxyethyl ethyl ether pendant arms were synthesized. Solubility trends indicated that solubilities in water or hydrocarbon solvents varied depending on the nature of the pendant arms. Binding constants for hydrophilic pincers were larger in general than their hydrophobic analogs. Significant synergistic binding effects for the ditopic hosts were not observed.

Redox-Inactive Metal Cations Modulate the Reduction Potential of the Uranyl Ion in Macrocyclic Complexes.

Capture and activation of the water-soluble uranyl dication (UO22+) remains a challenging problem, as few rational approaches are available for modulating the reactivity of this species. Here, we report the divergent synthesis of heterobimetallic complexes in which UO22+ is held in close proximity to a range of redox-inactive metals by a tailored macrocyclic ligand. Crystallographic and spectroscopic studies confirm assembly of homologous UVI(µ-OAr)2Mn+ cores with a range of mono-, di-, and trivalent Lewis acids (Mn+). Cyclic voltammetry data demonstrate that the UVI/UV reduction potential in these complexes is modulated over a span of 600 mV, depending linearly on the Lewis acidity of the redox-inactive metal with a sensitivity of 61 ± 9 mV/pKa unit. These findings suggest that interactions with Lewis acids could be effectively leveraged for rational tuning of the electronic and thermochemical properties of the 5f elements, reminiscent of strategies more commonly employed with 3d transition metals.

Synthesis and Reactivity Studies of a [Cp*Rh] Complex Supported by a Methylene-Bridged Hybrid Phosphine-Imine Ligand.

[Cp*Rh] complexes (Cp* = η 5-pentamethylcyclopentadienyl) supported by bidentate chelating ligands are useful in studies of redox chemistry and catalysis, but little information is available for derivatives bearing "hybrid" [P,N] chelates. Here, the preparation, structural characterization, and chemical and electrochemical properties of a [Cp*Rh] complex bearing the κ2-[P,N]-2-[(diphenylphosphino)methyl]pyridine ligand (PN) are reported. Cyclic voltammetry data reveal that [Cp*Rh(PN)Cl]PF6 (1) undergoes a chemically reversible, net two-electron reduction at -1.28 V vs. ferrocenium/ferrocene, resulting in generation of a rhodium(I) complex (3) that is stable on the timescale of the voltammetry. However, 1H and 31P{1H} NMR studies reveal that chemical reduction of 1 generates a mixture of products over a 1 h timescale; this mixture forms as a result of deprotonation of the methylene group of 1 by 3 followed by further reactivity. The analogous complex [Cp*Rh(PQN)Cl]PF6 (2; PQN = κ2-[P,N]-8-(diphenylphosphino)quinoline) does not undergo self-deprotonation or further reactivity upon two-electron reduction, confirming the reactivity of the acidic backbone methylene C-H bonds in the PN complexes. Comparison of the electrochemical properties 1 and 2 also shows that the extended conjugated system of PQN contributes to an additional ligand-centered redox event for 2 that is absent for 1.

Hydrogen-Bonding Linkers Yield a Large-Pore, Non-Catenated, Metal-Organic Framework with pcu Topology.

Pillared paddle-wheel-based metal-organic framework (MOF) materials are an attractive target as they offer a reliable method for constructing well-defined, multifunctional materials. A drawback of these materials, which has limited their application, is their tendency to form catenated frameworks with little accessible volume. To eliminate this disadvantage, it is necessary to investigate strategies for constructing non-catenated pillared paddle-wheel MOFs. Hydrogen-bonding substituents on linkers have been postulated to prevent catenation in certain frameworks and, in this work, we present a new MOF to further bolster this theory. Using 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid, BPDC-(NH2)2, linkers and dipyridyl glycol, DPG, pillars, we assembled a MOF with pcu topology. The new material is non-catenated, exhibiting large accessible pores and low density. To the best of our knowledge, this material constitutes the pcu framework with the largest pore volume and lowest density. We attribute the lack of catenation to the presence of H-bonding substituents on both linkers.

4,5-Diazafluorene and 9,9'-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes.

4,5-diazafluorene (daf) and 9,9'-dimethyl-4,5-diazafluorene (Me2daf) are structurally similar to the important ligand 2,2'-bipyridine (bpy), but significantly less is known about the redox and spectroscopic properties of metal complexes containing Me2daf as a ligand than those containing bpy. New complexes Mn(CO)3Br(daf) (2), Mn(CO)3Br(Me2daf) (3), and [Ru(Me2daf)3](PF6)2 (5) have been prepared and fully characterized to understand the influence of the Me2daf framework on their chemical and electrochemical properties. Structural data for 2, 3, and 5 from single-crystal X-ray diffraction analysis reveal a distinctive widening of the daf and Me2daf chelate angles in comparison to the analogous Mn(CO)3(bpy)Br (1) and [Ru(bpy)3]2+ (4) complexes. Electronic absorption data for these complexes confirm the electronic similarity of daf, Me2daf, and bpy, as spectra are dominated in each case by metal-to-ligand charge transfer bands in the visible region. However, the electrochemical properties of 2, 3, and 5 reveal that the redox-active Me2daf framework in 3 and 5 undergoes reduction at a slightly more negative potential than that of bpy in 1 and 4. Taken together, the results indicate that Me2daf could be useful for preparation of a variety of new redox-active compounds, as it retains the useful redox-active nature of bpy but lacks the acidic, benzylic C-H bonds that can induce secondary reactivity in complexes bearing daf.

Preparation, Characterization, and Electrochemical Activation of a Model [Cp*Rh] Hydride.

Monomeric half-sandwich rhodium hydride complexes are often proposed as intermediates in catalytic cycles, but relatively few such compounds have been isolated and studied, limiting understanding of their properties. Here, we report preparation and isolation of a monomeric rhodium(III) hydride complex bearing the pentamethylcyclopentadienyl (Cp*) and bis(diphenylphosphino)benzene (dppb) ligands. The hydride complex is formed rapidly upon addition of weak acid to a reduced precursor complex, Cp*Rh(dppb). Single-crystal X-ray diffraction data for the [Cp*Rh] hydride, which were previously unavailable for this class of compounds, provide evidence of the direct Rh-H interaction. Complementary infrared spectra show the Rh-H stretching frequency at 1986 cm-1. In contrast to results with other [Cp*Rh] complexes bearing diimine ligands, treatment of the isolated hydride with strong acid does not result in H2 evolution. Electrochemical studies reveal that the hydride complex can be reduced only at very negative potentials (ca. -2.5 V vs ferrocenium/ferrocene), resulting in Rh-H bond cleavage and H2 generation. These results are discussed in the context of catalytic H2 generation, and development of design rules for improved catalysts bearing the [Cp*] ligand.

Uniform, Binary Functionalization of a Metal-Organic Framework Material.

General routes to confined spaces of well-defined chemical composition and complex three-dimensional structure have long been sought by materials chemists. Here, we introduce metal-organic framework (MOF) materials as an ideal scaffold upon which such organized complexity can be built. Employing an orthogonal coordination strategy, we constructed a large-pore MOF material with two different modifiable linkers in well-defined positions relative to each other. The independent and quantitative covalent grafting of two distinct chemical groups onto these differently reactive linkers yielded a uniformly bifunctionalized MOF material. Not only does this methodology offer an efficient route via which the properties of well-defined microporous materials can be fine-tuned, but it also creates a solid-state platform for synthetically accessing constructs that better emulate the well-ordered intricacy of biological structures.

Structure and Reactivity of (µ-Oxo)dimanganese(III,III) and Mononuclear Hydroxomanganese(III) Adducts Supported by Derivatives of an Amide-Containing Pentadentate Ligand.

Mononuclear MnIII-hydroxo and dinuclear (µ-oxo)dimanganese(III,III) complexes were prepared using derivatives of the pentadentate, amide-containing dpaq ligand (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino- N-quinolin-8-yl-acetamidate). Each of these ligand derivatives (referred to as dpaq5R) contained a substituent R (where R = OMe, Cl, and NO2) at the 5-position of the quinolinyl group. Generation of the MnIII complexes was achieved by either O2 oxidation of MnII precursors (for [MnII(dpaq5OMe)]+ and [MnII(dpaq5Cl)]+ or PhIO oxidation (for [MnII(dpaq5NO2)]+). For each oxidized complex, 1H NMR experiments provided evidence of a water-dependent equilibrium between paramagnetic [MnIII(OH)(dpaq5R)]+ and an antiferromagnetically coupled [MnIIIMnIII(µ-O)(dpaq5R)2]2+ species in acetonitrile, with the addition of water favoring the MnIII-hydroxo species. This conversion could also be monitored by electronic absorption spectroscopy. Solid-state X-ray crystal structures for each [MnIIIMnIII(µ-O)(dpaq5R)2](OTf)2 complex revealed a nearly linear Mn-O-Mn core (angle of ca. 177°), with short Mn-O distances near 1.79 Å, and a Mn···Mn separation of 3.58 Å. X-ray crystallographic information was also obtained for the mononuclear [MnIII(OH)(dpaq5Cl)](OTf) complex, which has a short Mn-O(H) distance of 1.810(2) Å. The influence of the 5-substituted quinolinyl moiety on the electronic properties of the [MnIII(OH)(dpaq5R)]+ complexes was demonstrated through shifts in a number of 1H NMR resonances, as well as a steady increase in the MnIII/II cyclic voltammetry peak potential in the order [MnIII(OH)(dpaq5OMe)]+ < [MnIII(OH)(dpaq)]+ < [MnIII(OH)(dpaq5Cl)]+ < [MnIII(OH)(dpaq5NO2)]+. These changes in oxidizing power of the MnIII-hydroxo adducts translated to only modest rate enhancements for TEMPOH oxidation by the [MnIII(OH)(dpaq5R)]+ complexes, with the most reactive [MnIII(OH)(dpaq5NO2)]+ complex showing a second-order rate constant only 9-fold larger than that of the least reactive [MnIII(OH)(dpaq5OMe)]+ complex. These modest rate changes were understood on the basis of density functional theory (DFT)-computed p Ka values for the corresponding [MnII(OH2)(dpaq5R)]+ complexes. Collectively, the experimental and DFT results reveal that the 5-substituted quinolinyl groups have an inverse influence on electron and proton affinity for the MnIII-hydroxo unit.

Spontaneous Stereoselective Oxidation of Crystalline Avermectin B1a to Its C-8a-(S)-Hydroperoxide.

Prolonged storage of technical abamectin as well as avermectin B1a samples yielded a previously unknown derivative, designated here as compound 1. Detailed NMR analysis and X-ray crystallography allowed us to determine the structure of this compound and revealed the presence of a hydroperoxide group (-OOH) attached stereoselectively with configuration S to the C-8a carbon. This surprising result involves the formation of the peroxide bond in solid crystalline avermectin B1a upon exposure to air with no involvement of light or recognized catalytic factors and is consistent with a topotactic mechanism for the oxidation reaction. Compound 1 is stable in the absence of reducing agents and has potential as a starting point in structural modification of the tetrahydrofuran ring of avermectin B1a. It could also serve as a marker in assessing the quality of stored technical abamectin.

Trivalent Lewis Acidic Cations Govern the Electronic Properties and Stability of Heterobimetallic Complexes of Nickel.

Assembly of heterobimetallic complexes is synthetically challenging due to the propensity of ditopic ligands to bind metals unselectively. Here, we employ a novel divergent approach for selective preparation of a variety of bimetallic complexes within a ditopic macrocyclic ligand platform. In our approach, nickel is readily coordinated to a Schiff base cavity, and then a range of redox-inactive cations (M=Na+ , Ca2+ , Nd3+ , and Y3+ ) are installed in a pendant crown-ether-like site. This modular strategy allows access to complexes with the highly Lewis acidic trivalent cations Nd3+ and Y3+ , a class of compounds that were previously inaccessible. Spectroscopic and electrochemical studies reveal wide variations in properties that are governed most strongly by the trivalent cations. Exposure to dimethylformamide drives loss of Nd3+ and Y3+ from the pendant crown-ether site, suggesting solvent effects must be carefully considered in future applications involving use of highly Lewis acidic metals.