Homoleptic Diphosphacyclobutadiene Complexes [M(4-P2C2R2)2]x- (M=Fe, Co; x=0, 1),

[en] The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands is reported. Compounds [K([18]crown-6)(thf)2][Fe(h4- P2C2tBu2)2] (K1), [K([18]crown-6)-(thf)2][Co(h4-P2C2tBu2)2] (K2), and [K([18]crown-6)(thf)2][Co(h4- P2C2Ad2)2] (K3, Ad=adamantyl) were obtained from reactions of [K([18]crown-6)(thf)2][M(h4-C14H10)2] (M=Fe, Co) with tBuC P (1, 2), or with AdC P (3). Neutral sandwiches [M(h4-P2C2tBu2)2] (4: M=Fe 5: M= Co) were obtained by oxidizing 1 and 2 with [Cp2Fe]PF6. Cyclic voltammetry and spectro-electrochemistry indicates that the pairs [M(h4-P2C2tBu2)2] / [M(h4-P2C2tBu2)2] can be reversibly interconverted by one electron oxidation and reduction, respectively. Complexes 1–5 were characterized by multinuclear NMR, EPR (1 and 5), UV/Vis, and Mçssbauer spectroscopies (1 and 4), mass spectrometry (4 and 5), and microanalysis (1–3). The molecular structures of 1–5 were determined by usingX-ray crystallography. Essentially D2dsymmetric structures were found for all five complexes, which show the two 1,3-diphosphacyclobutadiene rings in a staggered orientation. Density functional theory calculations revealed the importance of covalent metal–ligand p bonding in 1–5. Possible oxidation state assignments for the metal atoms are discussed.

Disciplines :

Chemistry

Author, co-author :

Wolf, Robert

Ehlers, Andreas W

Khusniyarov, Marat M

Hartl, Frantisek

de Bruin, Bas

Long, Gary J

Grandjean, Fernande ; Université de Liège - ULiège > Département de physique > Département de physique

Schappacher, Falko M

Pottgen, Rainer

Slootweg, J. Chris

More authors (3 more)

Language :

English

Title :

Homoleptic Diphosphacyclobutadiene Complexes [M(4-P2C2R2)2]x- (M=Fe, Co; x=0, 1),

Publication date :

2010

Journal title :

Chemistry

ISSN :

0947-6539

eISSN :

1521-3765

Publisher :

Wiley

Volume :

Pages :

14322-14334

Peer reviewed :

Peer Reviewed verified by ORBi

Available on ORBi :

since 30 November 2012

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