Syntheses, Structures and Magnetic Properties of New Chalcogen‐Bridged Heterodimetallic Cluster Compounds with Heterocubane Structure

Abstract

The reaction of nickel, iron and cobalt complexes with MCl5 (M = Nb, Ta) and silylated chalcogen compounds in the presence of phosphane ligands yield the cluster compounds [Nb2Ni2S4Cl4(PPh3)2(CH3CN)2] (1), [Nb2Ni2Se4Cl4(PPh3)2(CH3CN)2] (2), [Ta2Ni2S4Br4(PPh3)2(CH3CN)2] (3), [Ta2Ni2Se4Br4(PPh3)2(CH3CN)2] (4), [Ni3S2(PMe3)6][Ta3NiS4(PMe3)4Cl6]2 (5), [Fe(dppm)2(CH3CN)2][NbFe3S4Cl3(dppm)(CH3CN)]2 (6) [dppm = (diphenylphosphanyl)methane], [Fe(dppm)2(CH3CN)2][TaFe3S4Cl3(dppm)(CH3CN)]2 (7), [FeCl(dppmSe)2][TaFe3Se4Cl3(dppm)(CH3CN)] (8) and [NbCo3Se4(PPh3)3(CH3CN)3][CoCl3(PPh3)] (9). The compounds (Et4N)3[NbFe2S4(SPh)4] (10) and (Et4N)3[NbFe2Se4(SPh)4] (11) were obtained by treating (Et4N)2[Fe(SPh)4] with Li3NbE4 (E = S, Se). (Et4N)3[Nb2Fe6S8(SPh)9] (12) was synthesized by adding FeCl2 to compound 10 used as starting material. (Et4N)3[Nb2Fe6Se8(SePh)9] (13) (which is isostructural to 12) was synthesized by treating FeCl2 with NaSetBu, NbCl5 and PhSeSiMe3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Reactivity of [Ni(cod)2][Al(ORF)4] towards Small Molecules and Elements

“…Furthermore, no other Ag‐S clusters bearing a similar constitution have been structurally characterized to date. In contrast, this structure pattern of 5 was reported for several Ni II compounds as shown in Table , disclosing distances, which are in good agreement . Lastly, these reasons confirm the accuracy of our determined molecular structure of 5 although X‐ray structure data possesses only low quality.…”

Systematic Approach for the Construction of Niobium and Tantalum Sulfide Clusters

“…To our knowledge, only the crystal structures of two homometallic M 4 O 4 (M = Nb, Ta) and a few heterometallic M 2 M′ 2 E 4 (M = Nb, Ta; M′ = Ni, Cu, Ag, E = S, Se) cube-type clusters have been reported to date, ,, complexes 5 – 8 then being the first group 5 homometallocubane M 4 S 4 complexes.…”

Ternary Mixed‐Valence Organotin Copper Selenide Clusters

“…The family of discrete metal chalcogenide clusters with a ternary inorganic core comprises a diversity of structural motifs and compositions, ranging from ligand‐stabilized neutral heterocubanes to huge anionic supertetrahedra, and from clusters of moderate size to compounds on a nanometer scale . These feature combinations of different transition metal atoms or different main group metal atoms, or both, or they combine atoms of transition metals and lanthanides …”