AustralieFrV1, Main, Exploration, bibRecord, 009049

Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(μ-CCCC)]

Identifieur interne : 009049 ( Main/Exploration ); précédent : 009048; suivant : 009050

Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(μ-CCCC)]

Auteurs : Michael I. Bruce [Australie] ; Karine Costuas [France] ; Thomas Davin [France] ; Jean-François Halet [France] ; Kathy A. Kramarczuk [Australie] ; Paul J. Low [Royaume-Uni] ; Brian K. Nicholson [Nouvelle-Zélande] ; Gary J. Perkins [Australie] ; Rachel L. Roberts [Royaume-Uni] ; Brian W. Skelton [Australie] ; Mark E. Smith [Royaume-Uni] ; Allan H. White [Australie]

Source :

Dalton Transactions [ 1477-9226 ] ; 2007.

RBID : ISTEX:EDCCBE15282208BAFA836FB4DE6483B5E22A5C2A

English descriptors

Abstract

The sequential conversion of [OsBr(cod)Cp*] (9) to [OsBr(dppe)Cp*] (10), [Os(CCH2)(dppe)Cp*]PF6 ([11]PF6), [Os(CCH)(dppe)Cp*] (12), [{Os(dppe)Cp*}2{μ-(CCH–CHC)}][PF6]2 ([13](PF6)2) and finally [{Os(dppe)Cp*}2(μ-CCCC)] (14) has been used to make the third member of the triad [{M(dppe)Cp*}2(μ-CCCC)] (M = Fe, Ru, Os). The molecular structures of [11]PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([15]PF6) and [Os(CCPh)(dppe)Cp*] (16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe ≈ Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(μ-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.

Url:

https://api.istex.fr/document/EDCCBE15282208BAFA836FB4DE6483B5E22A5C2A/fulltext/pdf

DOI: 10.1039/b712104k

Affiliations:

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<term>Bond order</term>
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<front><div type="abstract">The sequential conversion of [OsBr(cod)Cp*] (9) to [OsBr(dppe)Cp*] (10), [Os(CCH2)(dppe)Cp*]PF6 ([11]PF6), [Os(CCH)(dppe)Cp*] (12), [{Os(dppe)Cp*}2{μ-(CCH–CHC)}][PF6]2 ([13](PF6)2) and finally [{Os(dppe)Cp*}2(μ-CCCC)] (14) has been used to make the third member of the triad [{M(dppe)Cp*}2(μ-CCCC)] (M = Fe, Ru, Os). The molecular structures of [11]PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([15]PF6) and [Os(CCPh)(dppe)Cp*] (16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe ≈ Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(μ-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.</div>
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   |clé=     ISTEX:EDCCBE15282208BAFA836FB4DE6483B5E22A5C2A
   |texte=   Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(μ-CCCC)]
}}

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Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(μ-CCCC)]

Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(μ-CCCC)]

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