Assembly of Encapsulated Transition Metal Catalysts

Slagt, Vincent F.; Reek, Joost N. H.; Kamer, Paul C. J.; Leeuwen, Piet W. N. M. van

doi:10.1002/1521-3773(20011119)40:22<4271::aid-anie4271>3.3.co;2-8

Cited by 49 publications

(92 citation statements)

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“…111 A novel concept of encapsulating transition metal catalysts was introduced by Reek and co-workers. 112 The addition of zinc tetrakis(meso-phenyl)porphyrin to [Pd (45) 4 ] yielded the mono-phosphane palladium complex 46 (Chart 1), which is encapsulated by three zinc porphyrins, whereas the formation of complexes containing more phosphane ligands is prohibited as a result of steric congestion.…”

Section: Noncovalent Systemssupporting

confidence: 69%

Self‐Assembled Nanoreactors

et al. 2005

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Section: Noncovalent Systemssupporting

confidence: 69%

Self‐Assembled Nanoreactors

et al. 2005

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“…We previously introduced the ligandtemplate strategy for creating dynamic well-defined cavities around ligand-binding sites and the metal coordinated to such ligands 22 . Upon mixing tris-(meta-pyridyl)-phosphine ((m-py) 3 P) and three equivalents of Zn(II)tetraphenylporphyrin (ZnTPP) in toluene, the assembly forms by selective pyridyl-zinc coordination.…”

Section: Formation Of Capsulesmentioning

confidence: 99%

Capsule-controlled selectivity of a rhodium hydroformylation catalyst

et al. 2013

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Chemical processes proceed much faster and more selectively in the presence of appropriate catalysts, and as such the field of catalysis is of key importance for the chemical industry, especially in light of sustainable chemistry. Enzymes, the natural catalysts, are generally orders of magnitude more selective than synthetic catalysts and a major difference is that they take advantage of well-defined cavities around the active site to steer the selectivity of a reaction via the second coordination sphere. Here we demonstrate that such a strategy also applies for a rhodium catalyst; when used in the hydroformylation of internal alkenes, the selectivity of the product formed is steered solely by changing the cavity surrounding the metal complex. Detailed studies reveal that the origin of the capsule-controlled selectivity is the capsule reorganization energy, that is, the high energy required to accommodate the hydride migration transition state, which leads to the minor product.

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“…2 (see Table 1 for selected bond lengths and angles). Their coordination geometries • , b = 104.119(2) (8) are similar to those observed for related Rh I (Cl)(cod)(NHC) complexes.…”

Section: Catalyst Precursorsmentioning

confidence: 99%

“…10 One of the advantages is the relative ease with which large catalyst libraries can be prepared as it involves simple mixing of ligand building blocks that form the catalyst. We successfully demonstrated the viability of this approach in the hydroformylation of 1-octene leading to mainly branched aldehydes, 8 in the hydrogenation of challenging enamides 7e and in the palladium-catalyzed allylic alkylation.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular NHC ligands: on the influence of ZnII-templates on the activity of RhI(cod) complexes in ‘carbene polymerization’

Rubio

Jellema

Siegler³

et al. 2009

Dalton Trans.

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New RhI (cod) complexes of N-heterocyclic carbene ligands containing a pending pyridyl moiety for subsequent binding of Zn II -templates were designed for supramolecular catalyst control in 'carbene polymerization' reactions. Zn II -templates indeed have an influence on the yields and the polymer molecular weights (and weight distributions) produced by these 'supramolecular assemblies'. However, control experiments reveal that the effect of the Zn II -template on the polymerization results is general and not due to the assembly formation.

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Assembly of Encapsulated Transition Metal Catalysts

Cited by 49 publications

References 0 publications

Self‐Assembled Nanoreactors

Self‐Assembled Nanoreactors

Capsule-controlled selectivity of a rhodium hydroformylation catalyst

Supramolecular NHC ligands: on the influence of ZnII-templates on the activity of RhI(cod) complexes in ‘carbene polymerization’

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