A Series of Cyclopentadienyl Lanthanum Complexes with Metalloid Germanium Clusters.

A series of cyclopentadienyllanthanum complexes with the disilylated metalloid germanium cluster [Ge9(Hyp)2]2- [Hyp = Si(SiMe3)3] has been prepared and fully characterized. The synthetic procedure is based on the salt metathesis reaction of two different cyclopentadienyllanthanum diiodides CpLaI2 (Cp: Cp*, pentamethylcyclopentadienyl; Cpttt, 1,2,4-tri-tert-butylcyclopentadienyl) with K2[Ge9(Hyp)2] in tetrahydrofuran (THF) with a subsequent extraction with n-hexane. The composition of the obtained compounds and the mode of coordination of the germanium cluster to the rare-earth metal are strongly influenced by the steric demand of the cyclopentadienyl ligands and the crystallization conditions. The centrosymmetric dimeric compounds with the common formula [CpLa(solv)(η2,3-Ge9(Hyp)2)]2 [1, Cp = Cp*, solv-THF; 2, Cp = Cpttt, solv-NCCH2C(Me)NSiMe3] have been isolated by the slow evaporation of a n-hexane solution, while a mononuclear complex [CptttLa(THF)2(η3-Ge9(Hyp)2)] (4) was found by crystallization from THF. The repeated recrystallization of 1 from n-hexane afforded the asymmetric dimer [Cp*La(THF)(η2,3-Ge9(Hyp)2)][Cp*La(η2,3-Ge9(Hyp)2)] (3) with only one coordinated THF molecule.

[(thf)5Ln(Ge9{Si(SiMe3)3}2)] (Ln = Eu, Sm, Yb): Capping Metalloid Germanium Cluster with Lanthanides.

We report the synthesis of three neutral complexes with different coordination modes of a di-silylated metalloid germanium cluster to divalent lanthanides [(thf)5Ln(ηn-Ge9(Hyp)2)] (Ln = Yb (1, n = 1); Eu (2, n = 2, 3), Sm (3, n = 2, 3); Hyp = Si(SiMe3)3) by the salt metathesis of LnI2 with K2[Ge9(Hyp)2] in THF. The complexes were characterized by elemental analysis, nuclear magnetic resonance and UV-vis-NIR spectroscopy, and single-crystal X-ray diffraction. In thf solution, the formation of contact or solvate-separated ion pairs depending on the concentration is assumed. Compound 2 exhibits a blue luminescence typical for Eu2+. The solid-state magnetic measurements of compounds 2 and 3 confirm the presence of divalent europium and samarium, respectively.

Low-Coordinate Mixed Ligand NacNac Complexes of Rare Earth Metals.

We report the synthesis and characterization of two types of new mixed-ligand rare earth complexes: tetracoordinate (NacNacMes)Ln(BIANdipp) (Ln = Dy (1), Er (2) and Y (3)) and pentacoordinate (NacNacMes)Ln(APdipp)(THF) (Ln = Dy (4), Er (5) and Y (6)). The first three compounds were prepared by the reaction of [(BIANDipp)LnI] with potassium ß-diketiminate. The salt metathesis of ß-diketiminato-supported rare earth dichlorides (NacNacMes)LnCl2(THF)2 with sodium o-amidophenolate results in compounds 4-6. The crystal structures of complexes 1-6 were determined by single-crystal analysis. The combination of bulky monoanionic N-mesityl-substituted ß-diketiminates with sterically hindered redox-active ligands led to the very low coordination numbers of rare earths and strong distortion of the chelate ligands.

Oxidation of [Ge9{Si(SiMe3)3}3]- with LnI3 (Ln = Eu, Sm, Yb): Isomerism of Metalloid Germanium Clusters.

The oxidation of K[Ge9(Hyp)3] (Hyp = Si(SiMe3)3) with lanthanide triiodides LnI3 (Ln = Eu, Sm, Yb) leads to the formation of novel clusters with a Ge18-core isolated as a co-crystallizate of Ge*18(Hyp)6 (1a) and Ge18(Hyp)5(Si(SiMe3)2)(SiMe3) (1b). Clusters 1a and 1b differ distinctly from the known cluster Ge18(Hyp)6 (A), which has been found earlier in the reaction of K[Ge9(Hyp)3] with FeCl2 and now identified as an intermediate product in the production of compounds 1a and 1b. These three compounds A, 1a, and 1b are thus structural isomers being the first example of genuine isomerism in metalloid main-group cluster compounds.

Oxidative Coupling of [Ge9(Si(SiMe3)3)2]2- with f Elements.

We report the reactions of K2[Ge9(Hyp)2] (Hyp = Si(SiMe3)3) with (thf)3YbI3, ThI4, and UCl4, leading to the oxidative coupling of the metalloid germanium cluster to form the dimeric dianion [Ge18(Hyp)4]2-. The novel dimerized Ge18-cluster was isolated and characterized by single-crystal X-ray diffraction analysis as a component of ionic compounds [Yb(thf)6][Ge18(Hyp)4] (1) and [K(2.2.2-crypt)]2[Ge18(Hyp)4] (2) with two different counterions. The dihedral angle between two intact Ge9 cages depends on the counterions, which was also studied by quantum-chemical calculations.

The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand: Synthesis and Characterization of [LnCp*2 (RN=)2 S], Ln=Sm, Eu, Yb; R=SiMe3.

The first lanthanide complexes with a redox-active sulfur diimide ligand, [LnCp*2 (Me3 SiN=)2 S] (Ln=Sm, Eu, Yb; Cp*=η5 -C5 Me5 ), are reported. The complexes were synthesized by using [LnCp*2 (THF)2 ] and (Me3 SiN=)2 S and have been thoroughly characterized by single-crystal X-ray diffraction, EPR spectroscopy, UV/Vis/NIR electronic absorption spectroscopy and SQUID magnetometry. The results, as interpreted by CASSCF/SOC-RASSI calculations providing a non-perturbative treatment of spin-orbit coupling, indicate that these paramagnetic complexes are best described as Ln3+ and [(Me3 SiN=)2 S]-. adducts. As such, these complexes contain the first isolated and structurally characterized acyclic [(RN=)2 S]-. radical anions.

Activation of SO2 with [(η(5) -C5 Me5 )2 Ln(THF)2 ] (Ln=Eu, Yb) leading to dithionite and sulfinate complexes.

The reaction of decamethylytterbocene [(η(5) -C5 Me5 )2 Yb(THF)2 ] with SO2 at low temperature gave two new compounds, namely, the Yb(III) dithionite/sulfinate complex [{(η(5) -C5 Me5 )2 Yb(µ3 ,1κ(2) O(1,3) ,2κ(3) O(2,2',4) -S2 O4 )}2 {(η(5) -C5 Me5 )Yb(µ,1κO,2κO'-C5 Me5 SO2 )}2 ] (1) and the Yb(III) dithionite complex [{(η(5) -C5 Me5 )2 Yb}2 (µ,1κ(2) O(1,3) ,2κ(2) O(2,4) -S2 O4 )] (2). After extraction of 1, the mixture was heated to give the dinuclear tetrasulfinate complex [{(η(5) -C5 Me5 )Yb}2 (µ,κO,κO'-C5 Me5 SO2 )4 ] (3 a). In contrast, from the reaction of [(η(5) -C5 Me5 )2 Eu(THF)2 ] with SO2 only the tetrasulfinate complex [{(η(5) -C5 Me5 )Eu}2 (µ,κO,κO'-C5 Me5 SO2 )4 ] (3 b) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO2 molecules to form the dithionite anion S2 O4 (2-) ; and 2) nucleophilic attack of one metallocene C5 Me5 ligand on the sulfur atom of SO2 . The compounds presented are the first dithionite and sulfinate complexes of the f-elements.

Metalloid germanium cluster shears for lanthanide diiodides.

We report the synthesis and characterization of ionic compounds [(thf)4YbI]2[Ge9(Hyp)3]2 (1) and [(thf)5LnI]4[Ge9(Hyp)3]4 (Ln = Eu (2), Sm (3)), (Hyp = Si(SiMe3)3). All compounds were examined by UV-Vis spectroscopy and a blue luminescence of Eu2+ was found. The solid state magnetic measurements of complexes 2 and 3 confirmed the presence of divalent lanthanides.

Sterically hindered o-quinone annulated with dithiete: a molecule comprising diolate and dithiolate coordination sites.

A new stable sterically hindered o-quinone annelated with a 1,2-dithiete ring was prepared by using mild conditions. The skeleton of the compound comprises diolate and dithiolate functions that have the potential to bind metals leading to the corresponding complexes. The reactivity of this compound as a ligand with respect to both coordination sites was studied. Reactions with metals indicate that the o-quinone function is reduced in the first stage to give semiquinonate and catecholate complexes. The dithiolate coordination site was involved in the reaction in a few cases only after diolate was bound. A trinuclear manganese complex with coordination on both sites was obtained and characterized by EPR spectroscopy. The electrochemical study of this quinone fused with dithiete is reported.

(thf)2Ln(Ge9{Si(SiMe3)3}3)2 (Ln = Eu, Sm): the first coordination of metalloid germanium clusters to lanthanides.

We report the synthesis, structure and magnetic properties of the first rare earth complexes of metalloid group 14 clusters [(thf)2Ln(Ge9Hyp3)2] (Ln = Eu, Sm, Hyp = Si(SiMe3)3). X-Ray crystallographic analysis and DFT calculations reveal a novel η2-coordination mode of the Ge9Hyp3 units and a slight distortion of the Ge9 cage.

Deprotonation of Benzoxazolium Salt: Trapping of a Radical-Cation Intermediate.

The deprotonation of N-2,6-diisopropylphenyl-substituted benzoxazolium tetrafluoroborate 1 with NaH results in the formation of electron-rich diaminodioxaethylene 2. The radical cation salt 2·+·BF4- is found to be an intermediate product in the redox reaction leading from 1 to 2.

Europium and ytterbium complexes with o-iminoquinonato ligands: synthesis, structure, and magnetic behavior.

Complexes of divalent ytterbium (1) and europium (2) with a dianionic o-amidophenolate ligand were prepared by both the direct reduction of 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone (dpp-IQ) and the salt metathesis reaction of potassium o-amidophenolate with LnI2 (Ln = Yb, Eu). Oxidation of o-amidophenolates 1, 2 with one equivalent of dpp-IQ as well as the salt metathesis reaction of potassium o-iminosemiquinolate with LnI2 afforded ligand mixed-valent o-iminosemiquinonato-amidophenolato complexes of trivalent ytterbium (3) and europium (4). All novel complexes 1-4 were fully characterized, including the solid state structures of 1 and 2 determined by single crystal X-ray diffraction. The magnetic properties of paramagnetic 2-4 were examined.

Samarocene oxide: from an undesired decomposition product to a new reagent.

Samarocene oxide [Cp*2Sm-O-SmCp*2] is mostly considered as an undesired decomposition product of the well-established but highly air-sensitive samarocene, [Cp*2Sm(thf)2]. [Cp*2Sm-O-SmCp*2] is often formed by accidental exposure of [Cp*2Sm(thf)2] to air or wet solvents. We show here that [Cp*2Sm-O-SmCp*2] acts as a mild oxide base and thus is a valuable synthetic equivalent for "O(2-)". The reaction of [Cp*2Sm-O-SmCp*2] with the inorganic and organic anhydrides COS, CS2, SO2, SO3, Re2O7, and (PhC(O))2O at room temperature resulted in each case in an O(2-) insertion. The corresponding products were isolated as their samarium complexes.