Reference : Homoleptic Diphosphacyclobutadiene Complexes [M(4-P2C2R2)2]x- (M=Fe, Co; x=0, 1),
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
http://hdl.handle.net/2268/135653
Homoleptic Diphosphacyclobutadiene Complexes [M(4-P2C2R2)2]x- (M=Fe, Co; x=0, 1),
English
Wolf, Robert [> > > >]
Ehlers, Andreas W [> > > >]
Khusniyarov, Marat M [> > > >]
Hartl, Frantisek [> > > >]
de Bruin, Bas [> > > >]
Long, Gary J [> > > >]
Grandjean, Fernande mailto [Université de Liège - ULg > Département de physique > Département de physique >]
Schappacher, Falko M [> > > >]
Pottgen, Rainer [> > > >]
Slootweg, J. Chris [> > > >]
Lutz, Martin [> > > >]
Spek, Anthony L [> > > >]
Lammertsma, Koop [> > > >]
2010
Chemistry : A European Journal
Wiley
16
14322-14334
Yes (verified by ORBi)
International
0947-6539
1521-3765
[en] cobalt · iron · metalates ; phosphorus ; sandwich complexes
[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.
http://hdl.handle.net/2268/135653

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