Redox‐Switchable Phase Tags – Facile Mitsunobu Reactions using Ferrocenyl‐Tagged Triphenylphosphine

Fleckenstein, Christoph A.; Plenio, Herbert

doi:10.1002/adsc.200606024

Cited by 24 publications

(9 citation statements)

References 15 publications

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“…Redox-activeligandsoffer the possibility to easily modifyt he electronic properties of am etal complex.A sa ni nherent feature, they carry af ragment capable of gaining or losing electrons, with ac oncomitant change of the ligation properties, which meanst hat the oxidation/reduction of the ligand affects the Lewis acidity/basicity of both the ligand and the coordinated metal center. [4] Furthermore, uncommon reaction paths can be made available by al igand acting as an electron reser-voir. [2c, 5] In case the redox-active fragment of the ligand is am etal center, the ligand is frequently referredt oa saredoxactive metalloligand, that is, ac oordination complex as building block in lieu of simple organic ligands.…”

Section: Introductionmentioning

confidence: 99%

A Redox‐Switchable Germylene and its Ligating Properties in Selected Transition Metal Complexes

Walz

Moos

Garnier

et al. 2016

Chemistry A European J

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The synthesis, structure, and full characterization of a redox-switchable germylene based on a [3]ferrocenophane ligand arrangement, [Fc(NMes) Ge] (4), is presented. The mesityl (Mes)-substituted title compound is readily available from Fc(NHMes) (2) and Ge{N(SiMe ) } , or from the dilithiated, highly air- and moisture-sensitive compound Fc(NLiMes) ⋅3 Et O (3) and GeCl . Cyclic voltammetry studies are provided for 4, confirming the above-mentioned view of a redox-switchable germylene metalloligand. Although several 1:1 Rh and Ir complexes of 4 (5-7) are cleanly formed in solution, all attempts to isolate them in pure form failed due to stability problems. However, crystalline solids of [Mo(κ Ge-4) (CO) ] (8) and [W(κ Ge-4) (CO) ] (9) were isolated and fully characterized by common spectroscopic techniques (8 by X-ray diffraction). DFT calculations were performed on a series of model compounds to elucidate a conceivable interplay between the metal atoms in neutral and cationic bimetallic complexes of the type [Rh(κ E-qE)(CO) Cl] (qE=[Fc(NPh) E] with E=C, Si, Ge). The bonding characteristics of the coordinated Fc-based metalloligands (qE/qE ) are strongly affected upon in silico oxidation of the calculated complexes. The calculated Tolman electronic parameter (TEP) significantly increases by approximately 20 cm (E=C) to 25 cm (E=Si, Ge) upon oxidation. The change in the ligand-donating abilities upon oxidation can mainly be attributed to Coulombic effects, whereas an orbital-based interaction appears to have only a minor influence.

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Section: Introductionmentioning

confidence: 99%

A Redox‐Switchable Germylene and its Ligating Properties in Selected Transition Metal Complexes

Walz

Moos

Garnier

et al. 2016

Chemistry A European J

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“…Following the pioneering work of Wrighton et al, RSC has been applied to several areas of homogeneous catalysis, such as ring-opening polymerization, [3] ring-closing metathesis, [4] and the Mitsunobu reaction. [5] Thus catalysts have been switched to change the solubility of the catalyst (for catalyst recycling) [4b] or to modulate the activity of the transition metal (electronic communication between the redox-active group and the catalytic center). However, so far no reports have involved dendritic phosphane-containing ligands (Scheme 1).…”

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confidence: 99%

Redox Control of a Dendritic Ferrocenyl‐Based Homogeneous Catalyst

et al. 2014

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The application of a dendrimer in a redox-switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well-defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isomerization of the allylic alcohol 1-octen-3-ol. By adding a chemical oxidant or reductant, it was possible to reversibly switch the catalytic activity of the complexes. On oxidation, the ferrocenium moiety withdraws electron density from the phosphane, thereby lowering its basicity. The resulting electron-poor ruthenium center shows much lower activity for the redox isomerization and the reaction rate is markedly reduced.

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“…The catalyst can also be reactivated in situ upon addition of the reducing agent FcMe 8 . Later reports by Fleckenstein and Plenio and by Wang and co‐workers have further investigated the development of catalysts that display redox‐switchable solubility properties …”

Section: Redox‐switchable Catalystsmentioning

confidence: 99%

Dynamic Responsive Systems for Catalytic Function

Vlatković

Collins

Feringa

2016

Chemistry A European J

113

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Responsive systems have recently gained much interest in the scientific community in attempts to mimic dynamic functions in biological systems. One of the fascinating potential applications of responsive systems lies in catalysis. Inspired by nature, novel responsive catalytic systems have been built that show analogy with allosteric regulation of enzymes. The design of responsive catalytic systems allows control of catalytic activity and selectivity. In this Review, advances in the field over the last four decades are discussed and a comparison is made amongst the dynamic responsive systems based on the principles underlying their catalytic mechanisms. The catalyst systems are sorted according to the triggers used to achieve control of the catalytic activity and the distinct catalytic reactions illustrated.

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Redox‐Switchable Phase Tags – Facile Mitsunobu Reactions using Ferrocenyl‐Tagged Triphenylphosphine

Cited by 24 publications

References 15 publications

A Redox‐Switchable Germylene and its Ligating Properties in Selected Transition Metal Complexes

A Redox‐Switchable Germylene and its Ligating Properties in Selected Transition Metal Complexes

Redox Control of a Dendritic Ferrocenyl‐Based Homogeneous Catalyst

Dynamic Responsive Systems for Catalytic Function

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