A New Class of Diiron Arene Complexes with Disulfide and Diamine Bridges

Abd‐El‐Aziz, Alaa S.; Epp, Karen M.; Denus, Christine R. de; Fisher-Smith, Grant

doi:10.1021/om00018a024

Cited by 31 publications

(13 citation statements)

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“…This versatility is valuable in the investigation of synthetic routes for the functionalization of organic and polymeric compounds. In the past few years, we have been involved in the synthesis and characterization of polyaromatic ethers with or without pendant metallic moieties (44)(45)(46)(47). In this article, we report the addition of cyanide to a number of CpFe+ polyaromatic ether complexes.…”

Section: Cyanide Additionmentioning

confidence: 99%

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Nucleophilic addition to di- and poly-iron arene complex cations

Abd‐El‐Aziz¹,

Armstrong²,

Bernardin³

et al. 1996

Can. J. Chem.

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Abstract:Hydride and cyanide addition to a series of di-and polycyclopentadienyliron arene complex cations with etheric bridges is described. Reaction of the di-iron complexes with sodium borohydride resulted in the formation of a number of adducts. p-Methyl-and o,o-dimethylphenoxybenzene cyclopentadienyliron complexes were used as models in this study to allow for the characterization of the analagous di-iron complexes. The use of HH COSY and CH COSY NMR techniques enabled us to identify the isomeric nature of these adducts. The hydride addition results indicated that the etheric substituent had the predominant effect over the methyl group, leading to a higher addition ratio to the meta-, followed by the ortho-, then the para-positions. It was also clear that in the di-iron system, the hydride addition to each complexed arene ring took place independently. The addition of the cyanide anion to di-and poly-iron arene systems was more selective than that of the hydride anion. Reaction of sodium cyanide with p-methyl-or o-methyl-substituted arene complexes led to the formation of one adduct, with the cyanide being added to the meta position to the etheric bridges. However, cyanide addition to the di-iron complex, with a methyl substituent attached at the meta position of each complexed arene, led to the formation of a mixture of adducts. Cyanide addition to the poly-iron system withp-substituted arenes proved to be very selective, allowing for the formation of one adduct.Oxidative demetallation with 2,3-dichloro-5,6-dicyano-1.4-benzoquinone (DDQ) produced the uncomplexed polyaromatic ethers with cyano groups in a very good yield. des Cthers polyaromatiques non complexCs portant des groupes cyano.

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Section: Cyanide Additionmentioning

confidence: 99%

“…Starting complexes [I, 2, 5 , 7 , 9 , 12,13-281 were prepared by established procedures (45)(46)(47). Sodium borohydride (Alfa), DDQ (Aldrich), and sodium cyanide (Aldrich) are commercially available and were used without further purification.…”

Section: Reagentsmentioning

confidence: 99%

Nucleophilic addition to di- and poly-iron arene complex cations

Abd‐El‐Aziz¹,

Armstrong²,

Bernardin³

et al. 1996

Can. J. Chem.

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“…Aniline does not react with (PhCl)FeCp + but substitutes for a nitro group in (PhNO 2 )FeCp + [70]. Nitrogen heterocycles related to pyrrole were first converted to the corresponding sodium salts and then coupled with (chloroarene)FeCp + [71,72].…”

Section: S N Ar With Heteroatom Nucleophilesmentioning

confidence: 99%

(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

Semmelhack

Chlenov

2004

Topics in Organometallic Chemistry

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Transition metals coordinated to the pi system of arenes function as strong electronwithdrawing groups and favor nucleophilic addition to the arene to give cyclohexadienyl-metal complexes. The regioselectivity of addition is influenced in subtle and indirect ways, compared to the powerful effect on both reactivity and regioselectivity of electron-withdrawing groups attached to the sigma bond system of the arene. The intermediate cyclohexadienyl complexes can be processed in several ways, leading to several distinct synthesis methods. Useful reactivity is known for several metal systems and each is discussed for specific reaction types. The presence of a fluoro or chloro substituent on the arene allows an effective analog of classical S N Ar reactivity, with a wide range of nucleophiles including simple amines, alkoxides, and carbon anions. Another general process is the addition/protonation protocol, where a hydrogen substituent on the arene is replaced by a nucleophile. This opens new questions of regioselectivity since the typical arene ligand has several hydrogens which are candidates for substitution. The formation of five-and six-membered rings by both general mechanisms are known. Less general indirect mechanisms (e.g., tele substitution) have also been defined.

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“…[37][38][39] Scheme 4 illustrates the stepwise synthesis of this class of materials with as many as thirty-five pendent cyclopentadienyliron moieties. These organoiron oligomers and polymers were further functionalized through nucleophilic addition to the complexed arenes.…”

Section: Nucleophilic Aromatic Substitutionmentioning

confidence: 99%

Organometallic Polymers of the Transition Metals

Abd‐El‐Aziz

2002

Macromol. Rapid Commun.

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164

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This article provides a comprehensive review of the synthesis, properties and applications of organometallic polymers of the transition metals. The different classes of organometallic polymers are described according to their structural make‐up, as well as by their methods of synthesis. A number of examples of each class are given to emphasize the richness and diversity in these areas of research. In addition to linear polymers, hyperbranched, crosslinked, star and dendritic polymers are also described. The properties that transition metal‐containing organometallic polymers possess, as well as the applications that these materials have found in various domains are highlighted. magnified image

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A New Class of Diiron Arene Complexes with Disulfide and Diamine Bridges

Cited by 31 publications

References 0 publications

Nucleophilic addition to di- and poly-iron arene complex cations

Nucleophilic addition to di- and poly-iron arene complex cations

(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

Organometallic Polymers of the Transition Metals

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