Synthesis and Characterization of Pyridine-Armed Reinforced Macrocycles and Their Transition Metal Complexes as Potential Oxidation Catalysts

Oxidation catalysts stable in aqueous solution under both harsh pH\u27s and at high temperature would be environmentally friendly alternatives to current technologies. Transition metal complexes of tetraazamacrocycles reinforced with additional ethylene bridges have produced such oxidation catalysts. A controlling aspect of the usefulness of any metal catalyst is its set of oxidation and reduction potentials. Reversible redox processes that bracket a potential window within which useful oxidation of substrate molecules can occur are desirable. Though quite robust, and exhibiting reversible electrochemistry, some reinforced macrocycle complexes are not useful catalysts because their redox potentials are not in a desired potential range. An established method of modifying the electrochemical properties of a transition metal complex is to modify the ligand, which subsequently modifies the properties of its complexed metal ion. We wished to determine if the addition of pyridine pendant arms to the known reinforced macrocycle ligands would result in beneficial shifts in the redox potentials of their transition metal complexes. The resulting ligands must allow at least one open coordination site on the bound metal ion for oxidant and/or substrate binding. We have synthesized and characterized both cross-bridged and side-bridged cyclen and cyclam tetraazamacrocycles with pyridine pendant arms. Cobalt, nickel, copper, and zinc complexes were made. The synthesis and characterization of the ligands and the synthesis and characterization of their complexes will be presented

Synthesis, structural studies, and oxidation catalysis of the late-first-row-transition-metal complexes of a 2-pyridylmethyl pendant-armed ethylene cross-bridged cyclam

The first 2-pyridylmethyl pendant-armed ethylene cross-bridged cyclam ligand has been synthesized and successfully complexed to Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ cations. X-ray crystal structures were obtained for all six complexes and demonstrate pentadentate binding of the ligand with the requisite cis-V configuration of the cross-bridged cyclam ring in all cases, leaving a potential labile binding site cis to the pyridine donor for interaction of the complex with oxidants and/or substrates. The electronic properties of the complexes were evaluated using solid-state magnetic moment determination and acetonitrile solution electronic spectroscopy, which both agree with the crystal structure determination of high-spin divalent metal complexes in all cases. Cyclic voltammetry in acetonitrile revealed reversible redox processes in all but the Ni²⁺ complex, suggesting that catalytic reactivity involving electron-transfer processes is possible for complexes of this ligand. Kinetic studies of the dissociation of the ligand from the copper(II) complex under strongly acidic conditions and elevated temperatures revealed that the pyridine pendant arm actually destabilizes the complex compared to the parent cross-bridged cyclam complex. Screening for oxidation catalysis using hydrogen peroxide as the terminal oxidant for the most biologically relevant Mn²⁺, Fe²⁺, and Cu²⁺ complexes identified the Mn²⁺ complex as a potential mild oxidation catalyst worthy of continued development

Synthesis, structural studies, and oxidation catalysis of the manganese(II), iron(II), and copper(II) complexes of a 2-pyridylmethyl pendant armed side-bridged cyclam

The first 2-pyridylmethyl pendant armed structurally reinforced cyclam ligand has been synthesized and successfully complexed to Mn(2+), Fe(2+), and Cu(2+) cations. X-ray crystal structures were obtained for the diprotonated ligand and its Cu(2+) complex demonstrating pentadentate binding of the ligand with trans-II configuration of the side-bridged cyclam ring, leaving a potential labile binding site cis to the pyridine donor for interaction of the complex with oxidants and/or substrates. The electronic properties of these complexes were determined by means of solid state magnetic moment, with a low value of μ = 3.10 μ(B) for the Fe(2+) complex suggesting it has a trigonal bipyramidal coordination geometry, matching the crystal structure of the Cu(2+) complex, while the μ = 5.52 μ(B) value for the Mn(2+) complex suggests it is high spin octahedral. Cyclic voltammetry in acetonitrile revealed reversible redox processes in all three complexes, suggesting catalytic reactivity involving electron transfer processes are possible for these complexes. Screening for oxidation catalysis using hydrogen peroxide as the terminal oxidant identified the Fe(2+) complex as the oxidation catalysts most worthy of continued development

Synthesis, structural studies, kinetic stability, and oxidation catalysis of the late first row transition metal complexes of 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane

The first 2-pyridylmethyl pendant-armed ethylene cross-bridged cyclam ligand has been synthesized and successfully complexed to Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ cations. X-ray crystal structures were obtained for all six complexes and demonstrate pentadentate binding of the ligand with the requisite cis-V configuration of the cross-bridged cyclam ring in all cases, leaving a potential labile binding site cis to the pyridine donor for interaction of the complex with oxidants and/or substrates. The electronic properties of the complexes were evaluated using solid-state magnetic moment determination and acetonitrile solution electronic spectroscopy, which both agree with the crystal structure determination of high-spin divalent metal complexes in all cases. Cyclic voltammetry in acetonitrile revealed reversible redox processes in all but the Ni2+ complex, suggesting that catalytic reactivity involving electron-transfer processes is possible for complexes of this ligand. Kinetic studies of the dissociation of the ligand from the copper(II) complex under strongly acidic conditions and elevated temperatures revealed that the pyridine pendant arm actually destabilizes the complex compared to the parent cross-bridged cyclam complex. Screening for oxidation catalysis using hydrogen peroxide as the terminal oxidant for the most biologically relevant Mn2+, Fe2+, and Cu2+ complexes identified the Mn2+ complex as a potential mild oxidation catalyst worthy of continued development

Synthesis, Structural Studies, and Oxidation Catalysis of the Late-First-Row-Transition-Metal Complexes of a 2‑Pyridylmethyl Pendant-Armed Ethylene Cross-Bridged Cyclam

The first 2-pyridylmethyl pendant-armed ethylene cross-bridged cyclam ligand has been synthesized and successfully complexed to Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ cations. X-ray crystal structures were obtained for all six complexes and demonstrate pentadentate binding of the ligand with the requisite cis-V configuration of the cross-bridged cyclam ring in all cases, leaving a potential labile binding site cis to the pyridine donor for interaction of the complex with oxidants and/or substrates. The electronic properties of the complexes were evaluated using solid-state magnetic moment determination and acetonitrile solution electronic spectroscopy, which both agree with the crystal structure determination of high-spin divalent metal complexes in all cases. Cyclic voltammetry in acetonitrile revealed reversible redox processes in all but the Ni²⁺ complex, suggesting that catalytic reactivity involving electron-transfer processes is possible for complexes of this ligand. Kinetic studies of the dissociation of the ligand from the copper­(II) complex under strongly acidic conditions and elevated temperatures revealed that the pyridine pendant arm actually destabilizes the complex compared to the parent cross-bridged cyclam complex. Screening for oxidation catalysis using hydrogen peroxide as the terminal oxidant for the most biologically relevant Mn²⁺, Fe²⁺, and Cu²⁺ complexes identified the Mn²⁺ complex as a potential mild oxidation catalyst worthy of continued development

Synthesis, Structural Studies, and Oxidation Catalysis of the Late-First-Row-Transition-Metal Complexes of a 2‑Pyridylmethyl Pendant-Armed Ethylene Cross-Bridged Cyclam

The first 2-pyridylmethyl pendant-armed ethylene cross-bridged cyclam ligand has been synthesized and successfully complexed to Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ cations. X-ray crystal structures were obtained for all six complexes and demonstrate pentadentate binding of the ligand with the requisite cis-V configuration of the cross-bridged cyclam ring in all cases, leaving a potential labile binding site cis to the pyridine donor for interaction of the complex with oxidants and/or substrates. The electronic properties of the complexes were evaluated using solid-state magnetic moment determination and acetonitrile solution electronic spectroscopy, which both agree with the crystal structure determination of high-spin divalent metal complexes in all cases. Cyclic voltammetry in acetonitrile revealed reversible redox processes in all but the Ni²⁺ complex, suggesting that catalytic reactivity involving electron-transfer processes is possible for complexes of this ligand. Kinetic studies of the dissociation of the ligand from the copper­(II) complex under strongly acidic conditions and elevated temperatures revealed that the pyridine pendant arm actually destabilizes the complex compared to the parent cross-bridged cyclam complex. Screening for oxidation catalysis using hydrogen peroxide as the terminal oxidant for the most biologically relevant Mn²⁺, Fe²⁺, and Cu²⁺ complexes identified the Mn²⁺ complex as a potential mild oxidation catalyst worthy of continued development

An ethylene cross-bridged pentaazamacrocycle and its Cu2+ complex: constrained ligand topology and excellent kinetic stability

Rigid and topologically constrained ethylene cross-bridged tetraazamacrocycles have been increasingly utilised for thirty years as they form remarkably stable transition metal complexes for catalysis, biomedical imaging, and inorganic drug molecule applications. Extending these benefits to pentaazamacrocycles has been achieved and a first transition metal complex prepared and structurally characterized. This journal i

Expanding and quantifying the crystal chemistry of the flexible ligand 15aneN5

Tetraazamacrocycles have been very extensively exploited as transition metal ligands for a variety of purposes, including catalysis, medical imaging, pharmaceuticals, etc. However, the pentaazamacrocycles are much less commonly used for similar purposes because of poor availability, difficulties in their synthesis, and less well-known metal coordination properties. 1,4,7,10,13-pentaazacyclopentadane (15aneN5) was initially synthesized by a published synthetic route, which we simplified and shortened with minimal drop in yield. Eight different transition metal complexes were made using typical complexation methods. X-ray crystallography of multiple novel complexes yielded insight into the flexibility in coordination geometry of this interesting macrocycle as well as the first crystal structures of 15aneN5 with Cr3+, Mn3+, Fe3+, Co3+, Cu2+, and Ru2+. A parameter to quantify the coordination geometry adopted by the ligand was devised and applied to all known crystal structures of its metal complexes. Finally, oxidation of 15aneN5 to a novel diimine macrocycle was observed during complexation with ruthenium