Beyond hydrogen bonding: recent trends of outer sphere interactions in transition metal catalysis

Trouvé, Jonathan; Gramage‐Doria, Rafael

doi:10.1039/d0cs01339k

Cited by 64 publications

(37 citation statements)

References 177 publications

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“…Significant advances have been made in creating these artificial enzymes, as summarized [211][212][213][214][215][216][217][218][219][220][221] in several excellent reviews. It turns out that second-sphere coordination has been exploited widely as an emerging strategy for designing artificial enzymes by encapsulating catalysts inside molecular containers, leading to high efficiencies and excellent regio-and stereoselectivities being achieved at the catalytic centers.…”

Section: Catalysismentioning

confidence: 99%

Whither Second-Sphere Coordination?

et al. 2022

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The properties of coordination complexes are dictated by both the metals and the ligands. The use of molecular receptors as second-sphere ligands enables significant modulation of the chemical and physical properties of coordination complexes. In this Mini-Review, we highlight recent advances in functional systems based on molecular receptors as second-sphere coordination ligands, as applied in molecular recognition, synthesis of mechanically interlocked molecules, separation of metals, catalysis, and biomolecular chemistry. These functional systems demonstrate that second-sphere coordination is an emerging and very promising strategy for addressing societal challenges in health, energy, and the environment.

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Section: Catalysismentioning

confidence: 99%

Whither Second-Sphere Coordination?

et al. 2022

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“…On the other hand, less-conventional non-covalent interactions have also been exploited for substratepreorganization catalysis such as halogen bonding, pi interactions, amongst others. [47] An appealing type of non-covalent interaction is the kinetically-labile coordination between a metalloporphyrin and a polarcoordinating molecule (Figure 2, top). [48] In this type of interaction, the metal (i.e.…”

Section: Introductionmentioning

confidence: 99%

Mimicking Enzymes: Taking Advantage of the Substrate-Recognition Properties of Metalloporphyrins in Supramolecular Catalysis

Abuhafez¹,

Perennes²,

Gramage‐Doria³

2022

Synthesis

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The present review describes the most relevant advances dealing with supramolecular catalysis in which metalloporphyrins are employed as substrate-recognition sites in the second coordination sphere of the catalyst. The kinetically-labile interaction between metalloporphyrins (typically, those derived from zinc) and nitrogen- or oxygen-containing substrates is energetically comparable to those non-covalent interactions (i.e. hydrogen bonding) found in enzymes enabling substrate-preorganization. Much inspired from this host-guest phenomena, the catalytic systems described in this account display unique activities, selectivities and action modes difficult to reach applying purely covalent strategies.

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“…As transition metal complexes make up the vast majority of such catalysts, classical means for their modification through ligand design, the choice of and number of metal centres, and external influences such as light or electric current have received the majority of this research attention [1–6] . However, studies into ligand designs have also shown that metal‐based reactivity can be influenced by ligand‐based bond‐breaking and bond‐forming, secondary coordination sphere interactions, and ligand‐based redox reactions [7–10] . These are classed as cooperative modes of action.…”

Section: Introductionmentioning

confidence: 99%

“…[ 1 , 2 , 3 , 4 , 5 , 6 ] However, studies into ligand designs have also shown that metal‐based reactivity can be influenced by ligand‐based bond‐breaking and bond‐forming, secondary coordination sphere interactions, and ligand‐based redox reactions. [ 7 , 8 , 9 , 10 ] These are classed as cooperative modes of action. An emerging alternative to these more established classes of non‐innocent ligands is the installation of a single‐site ambiphilic centre that provides reactivity that is complementary to that of the transition metal.…”

Section: Introductionmentioning

confidence: 99%

Cooperativity in Transition Metal Tetrylene Complexes

Somerville

Campos

2021

Eur J Inorg Chem

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Cooperative reactivity between transition metals and ligands, or between two metals, has created significant opportunities for the development of new transformations that would be difficult to carry out with a single metal. Here we explore cooperativity between transition metals and divalent heavier group 14 elements (tetrylenes), a less‐explored facet of the field of cooperativity. Tetrylenes combine their strong σ‐donor properties with an empty p‐orbital that can accept electron density. This ambiphilicity has allowed them to form metal tetrylene and metallotetrylene complexes that place a reactive site adjacent to the metal. We have selected examples to demonstrate what has been achieved so far regarding cooperative reactivity, as this already spans metal‐, tetrylene‐ or multi‐site‐centred bond cleavage, cycloaddition, migration, metathesis, and insertion. We also highlight some challenges that need to be overcome for this cooperativity to make it to catalysis.

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Beyond hydrogen bonding: recent trends of outer sphere interactions in transition metal catalysis

Abstract: The implementation of interactions beyond hydrogen bonding in the 2nd coordination sphere of transition metal catalysts is rare. However, it has already shown great promise in last 5 years, providing new tools to control the activity and selectivity as here reviewed.

Cited by 64 publications

References 177 publications

Whither Second-Sphere Coordination?

Whither Second-Sphere Coordination?

Mimicking Enzymes: Taking Advantage of the Substrate-Recognition Properties of Metalloporphyrins in Supramolecular Catalysis

Cooperativity in Transition Metal Tetrylene Complexes

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