A triple-decker complex of tungsten, [(Cp*W){μ-η:η-BHCo(CO)}(H)] (; Cp* = η-CMe), with a planar middle deck has been isolated by thermolysis of an in situ formed intermediate from the reaction of Cp*WCl and LiBH with Co(CO). In addition, we have also isolated another triple-decker complex, [(Cp*W){μ-η:η-BHFe(CO)}(H)] (), having a puckered central ring, from a similar reaction with Fe(CO). Clusters and are unprecedented examples of a triple-decker complex having a 24-valence electron with bridging hydrogen atoms.
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The synthesis of the cluster complexes [(Cp'''Co)(μ,η:η:η-E)(μ-E)] (E=P (3), As (4)) starting from the anionic triple-decker complexes [K(18cr6)(dme)][(Cp'''Co)(μ,η:η-E)] (E=P (1), As (2)) by electrophilic quenching with the Co dimer [(Cp'''CoCl)] is reported. Both complexes show a distinct redox chemistry, which was first investigated by cyclic voltammetry. Subsequently, the monoanions [K(L)(sol)][(Cp'''Co)(μ,η:η:η-E)(μ-E)] (E=P, L=18cr6, sol=dme, n=2 (5), E=As, L=2,2,2-crypt, n=0 (6)), the monocations [(Cp'''Co)(μ,η:η:η-E)(μ-E)][FAl] (E=P (7), As (8)) and the dications [(Cp'''Co)(μ,η:η:η-E)][TEF] (E=P (9), As (10)) could be realized experimentally and isolated in moderate to good yields.
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Department of Chemistry, University of Wrocław, 14 F. Joliot-Curie, Wrocław 50-383, Poland.
The reaction of fluoride anions with mononuclear rare-earth(III) complexes of the hexaazamacrocycle derived from 2,6-diformylpyridine and ethylenediamine affords trinuclear coordination compounds . The X-ray crystal structures of these complexes show triplex cationic complexes where the three roughly parallel macrocyclic lanthanide(III) units are linked by bis-μ-F bridges. The detailed analysis of the photophysical properties of the and complexes reveals different temperature dependence of luminescence intensity and luminescence decay time of the Eu(III) and Tb(III) derivatives.
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Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Kaiserstr. 12, 76131 Karlsruhe, Germany.
To study the influence of heteroatoms on the photophysical properties of divalent Eu and Sr complexes, the synthesis of the phospholyl and arsolyl compounds [{(Dtp)(thf)M}{μ-η:η-CH}] (M = Eu and Sr; Dtp = 3,4-dimethyl-2,5-bis(-butyl)phospholyl) and [{(Dtas)(thf)M}{μ-η:η-CH}] (M = Eu and Sr; Dtas = 3,4-dimethyl-2,5-bis(-butyl)arsolyl) is reported. Organometallic compounds of divalent europium with P and As heterocyclic ligands have not been described previously. They were prepared by salt elimination reactions from potassium phospholyl or arsolyl, KCH, and EuI(thf) or SrI.
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Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, D-76131 Karlsruhe, Germany.
The first structurally characterized organometallic multidecker sandwich complexes featuring a cycloheptatrienyl ring (Cht, CH) in the coordination sphere are presented. The synthesis of inverse sandwich complexes of the rare earth elements Y and Er with a bridging cycloheptatrienyl ligand of the type [(thf)(BH)Ln(μ-η:η-Cht)Ln(BH)(thf)] is described first. The subsequent introduction of the Cot ligand (Cot = 1,4-(PrSi)CH) into the coordination sphere of the rare earth cations resulted in the isolation of unprecedented triple-decker compounds with the formula [(thf)K{(η-Cot)Ln}(μ-η:η-Cht)], bearing a seven-membered aromatic carbon ring as a middle deck.
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Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, 76131, Karlsruhe.
Herein, we present the first report on the synthesis of rare-earth complexes featuring a 9,10-diborataanthracene ligand. This 14-π-electron ligand is highly reductive and was previously used in small-molecule activation. Salt elimination reactions between dipotassium 9,10-diethyl-9,10-diborataanthracene [K(DEDBA)] and [Ln(η-Cot)(BH)(thf)] (Cot=1,4-(PrSi)CH) in a 1 : 1 ratio yielded heteroleptic sandwich complexes [K(η-Cot)Ln(η-DEDBA)] (Ln=Y, Dy, Er).
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