Polycyclooctadiene Complexes of Rhodium(I): Direct Access to Organometallic Nanoparticles

Mavila, Sudheendran; Diesendruck, Charles E.; Linde, Sivan; Amir, Liron; Shikler, Rafi; Lemcoff, N. Gabriel

doi:10.1002/anie.201300362

Cited by 86 publications

(78 citation statements)

References 44 publications

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“…31 UPy dimerization has been used to study the effect of several variables in SCNP formation. 61 Another example involves acac functionalized polymers containing copper(II) as a bridging metal for catalytic purposes. 57 Benzene-1,3,5-tricarboxamide (BTA) has been exploited in the field of supramolecular chemistry for its ability to form helical assemblies via hydrogen bonding; 68 consequently, it has also found use in SCNP synthesis.…”

Section: Non-covalent Chemistrymentioning

confidence: 99%

A brief user's guide to single-chain nanoparticles

et al. 2015

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In this review we outline the various methods that have been explored to synthesize architecturally defined nanoparticles from discrete polymer chains, summarize the methods of characterization that are required to prove their formation and probe their morphology, and introduce a number of potential applications that are being explored currently. Given the small size of the nanostructures produced by these methods and the relative ease with which they can be tailored to specific end use applications it is likely such efforts will intensify in the coming years. So far, simple chemistry has been utilized and high-level characterization and modeling studies have been applied to understand the process by which these particles form and how they behave, both in the bulk and in solution. Although impossible to predict where this work will lead, we hope this "user's guide" will prove useful to the community as research on singlechain nanoparticles continues to evolve.From left to right:

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Section: Non-covalent Chemistrymentioning

confidence: 99%

A brief user's guide to single-chain nanoparticles

et al. 2015

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“…[5][6][7] In the past, bioinspired SCNPs have been typically synthesized via hydrogen-or covalent bonding in order to mimic biomacromolecules. [10][11][12][13] While metal complexes,i nt he first place, operate as triggers for the chain-collapse,t heir embedding into the SCNP-structure additionally allows them to function, for example,a sc atalytic centers. [10][11][12][13] While metal complexes,i nt he first place, operate as triggers for the chain-collapse,t heir embedding into the SCNP-structure additionally allows them to function, for example,a sc atalytic centers.…”

mentioning

confidence: 99%

Platinum(II)‐Crosslinked Single‐Chain Nanoparticles: An Approach towards Recyclable Homogeneous Catalysts

et al. 2017

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We introduce the synthesis and in-depth characterization of platinum(II)-crosslinked single-chain nanoparticles (Pt -SCNPs) to demonstrate their application as a recyclable homogeneous catalyst. Specifically, a linear precursor copolymer of styrene and 4-(diphenylphosphino)styrene was synthesized via nitroxide-mediated polymerization. The triarylphosphine ligand moieties along the backbone allowed for the intramolecular crosslinking of single chains via the addition of [Pt(1,5-cyclooctadiene)Cl ] in dilute solution. The successful formation of well-defined Pt -SCNPs was evidenced by size exclusion chromatography, dynamic light scattering, nuclear magnetic resonance ( H, P{ H}, Pt), and diffusion-ordered spectroscopy. Finally, the activity of the Pt -SCNPs as homogeneous, yet recyclable catalyst was successfully demonstrated using the example of the amination of allyl alcohol.

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“…Indeed, these folded/collapsed soft nanostructures have gained increasing attention for the development of functional materials in the fields of nanomedicine, protein mimicry, and catalysis . In the catalysis field, the design of supported organometallic catalysts aims to emulate the unique features of (metallo)enzymes, such as structural complexity, compartmentalized functions, and site isolation . Previous work in the area has typically focused on the formation of SCNPs by hydrogen or covalent bonding between supported orthogonal functions .…”

Section: Methodsmentioning

confidence: 99%

Catalytically Active N‐Heterocyclic Carbene Release from Single‐Chain Nanoparticles Following a Thermolysis‐Driven Unfolding Strategy

Garmendia

Lawrenson

Arno

et al. 2019

Macromol. Rapid Commun.

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The need for efficient, tailor‐made catalysts has inspired chemists to design synthetic macromolecular architectures for selective catalysis. To this purpose, herein the synthesis and in‐depth characterization of Ag(I)‐crosslinked single‐chain nanoparticles (SCNPs) is reported and their application as catalysts is demonstrated. Specifically, a copolymer of styrenic benzimidazolium chloride is synthesized as a linear precursor via reversible addition‐fragmentation chain‐transfer polymerization. Metalation of the benzimidazolium moieties by Ag(I) resulted in the intramolecular cross‐linking of single chains via the formation of silver‐N‐heterocyclic carbene (Ag‐NHC) linkages under dilute conditions. The successful formation of well‐defined, robust SCNPs is evidenced by size‐exclusion chromatography, dynamic light scattering, nuclear magnetic resonance spectroscopy, and transmission electron microscopy. Finally, it is demonstrated that the Ag‐SCNPs can be used as NHC pre‐catalysts, by first indirectly evidencing the formation of the corresponding unfolded NHC‐CS2 polybetaine and then organocatalysing a benzoin condensation reaction.

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Polycyclooctadiene Complexes of Rhodium(I): Direct Access to Organometallic Nanoparticles

Cited by 86 publications

References 44 publications

A brief user's guide to single-chain nanoparticles

A brief user's guide to single-chain nanoparticles

Platinum(II)‐Crosslinked Single‐Chain Nanoparticles: An Approach towards Recyclable Homogeneous Catalysts

Catalytically Active N‐Heterocyclic Carbene Release from Single‐Chain Nanoparticles Following a Thermolysis‐Driven Unfolding Strategy

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