Hexahydrozirconation<i>versus</i>Hexahydroboration Routes to Hexaiodo Tentacled Aromatic Iron Sandwiches

Moulines, Françoise; Djakovitch, L.; Fillaut, Jean‐Luc; Astruc, Didier

doi:10.1055/s-1992-21265

Cited by 17 publications

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“…The hexaalkene is also an excellent starting point for further syntheses, especially using hydroelementation reactions. Hydrosilylation reactions catalyzed by Speir's reagent led to long-chain hexasilanes [46], and hydrozirconation has also been achieved using [Cp 2 Zr(H)(Cl)] [47]. The hexazirconium compound thus obtained is an intermediate for the synthesis of the hexaiodo derivative (Scheme 10) [47].…”

Section: 3mentioning

confidence: 99%

Activation of Simple Arenes by the CpFe ⁺ Group and Applications to the Synthesis of Dendritic Molecular Batteries

Astruc

Nlate

Ruiz

2002

Modern Arene Chemistry

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The CpFe þ -induced polyfunctionalization of polymethylbenzenes under ambient conditions gives virtually quantitative yields of CpFe þ (h 6 -arene)-centered stars and dendritic cores on a large scale. From the chlorotoluene complex, mild nucleophilic reaction with ethanol in the presence of K 2 CO 3 followed by mild reaction with allyl bromide in the presence of tBuOK gives a 60 % yield of the triallyl phenol dendron p-HOC 6 H 4 C(allyl) 3 . This dendron and its functionalized derivatives have been used as building blocks for the divergent synthesis of large dendrimers and for the convergent synthesis of nonafunctional dendrons including dendrons bearing ferrocenylsilyl termini on their branches. The various dendrimers, with branch numbers of up to 243 in theory, have been decorated with ferrocenyl groups, and polyaminodendrimers have been functionalized with ferrocenyl, cobaltocenyl, and CpFe þarene moieties. The generation or isolation of two redox states of these metallodendrimers and electron-transfer reactions illustrate their function as molecular electron reservoirs or molecular batteries. 12.1Scheme 1. Principle and general steps of the CpFe þ -induced activation of arenes by temporary complexation.12.2 General Features of the CpFe þ Activation of Arenes 401

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Section: 3mentioning

confidence: 99%

Activation of Simple Arenes by the CpFe ⁺ Group and Applications to the Synthesis of Dendritic Molecular Batteries

Astruc

Nlate

Ruiz

2002

Modern Arene Chemistry

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“…Synthetic applications are shown in Schemes 14 and 15. [43][44][45] With allyl bromide, the perallylation of the hexamethylbenzene ligand can be continued until dodecaallylation involving 12 sequences (24 reactions altogether), in which [FeCp(C 6 Me 6 )][PF 6 ] is a reservoir of 12 protons. The resulting dodecaallylated complex and closely related ones can be considered as the first organometallic dendrimers.…”

Section: Synthetic Applications Of the Complexes [Fecp(η 6arene)][pf ...mentioning

confidence: 99%

“…These facile reactions are accessible for benzylation and allylation 46 and are thus suitable for immediate application in synthesis. Indeed, polyallyl cores can be easily transformed into poly-primary alcohols by regiospecific hydroboration using disiamylborane and oxidation using H 2 O 2 /OH -(Scheme 14), 38,43,44 and polybenzyl cores can be regioselectively acylated (Scheme 15) 45 and chlorocarbonylated in para positions (Scheme 18). 36 An example of an application is represented in Scheme 18, where the octabenzylation and subsequent chlorocarbonylation reactions are used to introduce 24 amidofer-rocene and 24 [Cp*Fe(η 6 -N-anilino-)] termini on the branches of dendrimers.…”

Section: Synthetic Applications Of the Complexes [Fecp(η 6arene)][pf ...mentioning

confidence: 99%

Electron and Proton Reservoir Complexes: Thermodynamic Basis for C−H Activation and Applications in Redox and Dendrimer Chemistry

Astruc

2000

Acc. Chem. Res.

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This Account focuses on fundamental aspects and applications of the concept of "electron and proton reservoirs". Permethylated electron reservoir iron sandwich complexes, which were known to be excellent reducing agents in their neutral 19e Fe(I) form, have recently been shown to be stable strong oxidants in their dicationic 17e Fe(III) form. Thermodynamic, mechanistic, and synthetic aspects of the redox chemistry of these and related organoiron complexes are summarized. Proton reservoir properties of these complexes are due to enhanced acidity in their cationic form and result in an original type of activation: perfunctionalization leading to dendritic cores and useful metallodendrimers of variable topology.

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“…[79] However, because of the nature of the boranes that were used, such as catecholborane, 9-bbn and HBBr 2 ·SMe 2 , the boron side-arms are only weakly acidic, and no interactions at all are observed with either the metal centre or the carbonyl ligands. A similar strategy has been used for the synthesis of complexes 101 [80] and 102, [81] whereas complex 103 was obtained by the coordination of the areneborane on Cr(CO) 6 . [82] Scheme 19.…”

Section: Modification Of Bound Moieties B-h Activation On Hydrotris(mmentioning

confidence: 99%

Coordination Chemistry of Neutral (L_n)–Z Amphoteric and Ambiphilic Ligands

2008

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HexahydrozirconationversusHexahydroboration Routes to Hexaiodo Tentacled Aromatic Iron Sandwiches

Cited by 17 publications

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Activation of Simple Arenes by the CpFe ⁺ Group and Applications to the Synthesis of Dendritic Molecular Batteries

Activation of Simple Arenes by the CpFe ⁺ Group and Applications to the Synthesis of Dendritic Molecular Batteries

Electron and Proton Reservoir Complexes: Thermodynamic Basis for C−H Activation and Applications in Redox and Dendrimer Chemistry

Coordination Chemistry of Neutral (L_n)–Z Amphoteric and Ambiphilic Ligands

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HexahydrozirconationversusHexahydroboration Routes to Hexaiodo Tentacled Aromatic Iron Sandwiches

Cited by 17 publications

References 0 publications

Activation of Simple Arenes by the CpFe + Group and Applications to the Synthesis of Dendritic Molecular Batteries

Activation of Simple Arenes by the CpFe + Group and Applications to the Synthesis of Dendritic Molecular Batteries

Electron and Proton Reservoir Complexes: Thermodynamic Basis for C−H Activation and Applications in Redox and Dendrimer Chemistry

Coordination Chemistry of Neutral (Ln)–Z Amphoteric and Ambiphilic Ligands

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Activation of Simple Arenes by the CpFe ⁺ Group and Applications to the Synthesis of Dendritic Molecular Batteries

Activation of Simple Arenes by the CpFe ⁺ Group and Applications to the Synthesis of Dendritic Molecular Batteries

Coordination Chemistry of Neutral (L_n)–Z Amphoteric and Ambiphilic Ligands