Novel Templating Effect in the Macrocyclization of Functionalized Diynes by Zirconocene Coupling

Nitschke, Jonathan R.; Tilley, T. Don

doi:10.1002/1521-3773(20010601)40:11<2142::aid-anie2142>3.0.co;2-3

Cited by 41 publications

(2 citation statements)

References 20 publications

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“…Multinuclear, especially trinuclear titanium or zirconium complexes are known, [22][23][24][25][26] but these complexes are not formed by self-assembly and the metal atoms do not occupy the vertices of the molecular architectures. Here, the increased steric demand hinders the formation of rectangles or squares.…”

Section: Resultsmentioning

confidence: 99%

Self‐Assembly Reactions To Form Multinuclear Zirconium(III) and Titanium(III) Complexes with Imidazole Derivatives as Bridging Ligands

et al. 2018

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Self-assembly reactions with low valent early transition metals, leading to neutral multinuclear complexes are rare. Mostly late transition metals like Pt, Pd or Ru together with Nheterocycles or O-donor-based ligands are used to form supramolecular coordination complexes. This paper reports on selfassembly reactions of low valent titanocene and zirconocene units and five-membered N-heterocycles as bridging ligands. These reactions lead to novel molecular triangles and rectangles with the metal centers marking the vertices. Five different imidazole derivatives and four different metallocene precursors were used. For the first time, molecular triangles and architec-Scheme 1. Molecular quadrangle with pyrazine I and 4,4′-bipyridine II and a combination of both III as bridging ligands.[a]

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Section: Resultsmentioning

confidence: 99%

Self‐Assembly Reactions To Form Multinuclear Zirconium(III) and Titanium(III) Complexes with Imidazole Derivatives as Bridging Ligands

et al. 2018

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“…Similar to Th, U possesses a larger ionic radius and lower charge density in comparison with Zr and other transition metals, allowing for coordination with nitrogenous ligands. − To date, there have been no reports of extended metal–organic structures containing the Zr–N bond, for example despite Zr–N bonds detected in the more flexible structures of molecular complexes. − The mentioned role of ionic radius and Lewis acidity as structure-directing variables can be further supported by turning to a different class of inorganic materials, POMs. While MOFs are composed of both inorganic subunits and organic linkers, POMs are purely inorganic compounds, which can shed light on the intrinsic effects of ionic interactions and acidity on material structure without the complicating influence of organic compounds …”

Section: Synthetic Aspects Of Zr- U- and Th- Compoundsmentioning

confidence: 99%

Mining for Metal–Organic Systems: Chemistry Frontiers of Th-, U-, and Zr-Materials

Park,

Lim,

Thaggard

et al. 2024

J. Am. Chem. Soc.

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The conceptual framework presented in this Perspective overviews the design principles of innovative thorium-based materials that could address urgent needs of the medicinal, nuclear energy, and waste remediation sectors from the lens of zirconium and uranium analogs. We survey the intersections of Zr, Th, and U chemistry with a focus on how the intrinsic behavior of each metal translates to broader material properties, including, but not limited to, structural and topological diversity, preferential metal− ligand binding, and reactivity. On the example of several classes of materials, including organometallic complexes, polyoxometalates, and the primary focus of this Perspective, metal−organic frameworks (MOFs), the design principles that govern the preparation of Zr-, Th-, and U-compounds, including oxophilicity, variation in oxidation states, and stable coordination environments have been considered. Further, we highlight how the impact of the mentioned variables may shift throughout the progression from discrete molecular systems to extended structures. We discuss the common assumption that zirconium-organic materials are typically considered a close analog of thorium-based congeners in areas such as material design and preparation. Through consideration of fundamental chemistry principles, we shed light on the relationships between Zr-, Th-, and U-based materials and highlight how a critical analysis of their distinct properties can be used to target a desired material performance. As a result, we provide a detailed understanding of Th-based materials chemistry by anchoring their fundamental properties between two well-studied reference points, zirconium-and uranium-containing analogs.

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Di-n-butylbis(cyclopentadienyl)zirconium

Negishi

Novák

2005

Encyclopedia of Reagents for Organic Synthesis

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Novel Templating Effect in the Macrocyclization of Functionalized Diynes by Zirconocene Coupling

Cited by 41 publications

References 20 publications

Self‐Assembly Reactions To Form Multinuclear Zirconium(III) and Titanium(III) Complexes with Imidazole Derivatives as Bridging Ligands

Self‐Assembly Reactions To Form Multinuclear Zirconium(III) and Titanium(III) Complexes with Imidazole Derivatives as Bridging Ligands

Mining for Metal–Organic Systems: Chemistry Frontiers of Th-, U-, and Zr-Materials

Di-n-butylbis(cyclopentadienyl)zirconium

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