0000000000444986
AUTHOR
Patrick Schwarz
Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co 9 Te 6 (CO) 8 Clusters (Eur. J. Inorg. Chem. 12/2008)
The cover picture shows an organometallic electron sponge and an elephant-ear sponge in the background (photo by F. and J. Burek, National Marine Sanctuaries). The electronic flexibility of the cobalt-centered cubic [Co9Te6(CO)8]n cluster ([3]n) in the central circle is expressed by differently charged states (n = 1+ to 5–). Starting from the upper left corner of our graphic in a clockwise direction, neutral [Co9Te6(CO)4(PPh3)4], structurally diverse networks of [Ph3PNPPh3][3] and [Ph3PNPPh3]2[3] salts and the core of the [Co9Te3{ν5-Cp′2Nb(CO)Te}3(CO)8] cluster as a pseudo-protonated representative of the [3]3– anion are shown. Details of the structural, electrochemical and theoretical prop…
[{(C5Me5)2Nb}2PdTe4], a heterometallic palladium telluride cluster with a planar PdTe4 fragment
Abstract The reaction of [ Cp 2 ∗ Nb ( Te 2 H ) ] (Cp∗ = η5-C5Me5) with [Pd(DBA)2] (DBA = dibenzylidenacetone) and dppm (bis(diphenylphosphanyl)methane) gave the new tetratelluropalladate cluster [ ( Cp 2 ∗ Nb ) 2 PdTe 4 ] (1), which has been characterised by means of elemental analysis, FD-MS and X-ray crystallography. The structure of compound 1 contains a planar PdTe4 rectangle to which two niobocene groups are coordinated. DFT calculations on the hypothetical [PdTe4]2− anion and comparison of the results with those of the W and Ni homologues show that the planar arrangement of Te ligands in 1 is due to the intrinsic property of the central Pd atom.
Fragmentation reactions of realgar caused by early transition metal hydrides
Abstract The reaction of realgar with [Cp′2MH3] in boiling toluene gave [Cp′2M2As2S6] (Cp′ = t-BuC5H4; M = Nb: 1; Ta: 2), while [Cp2WH2] (Cp = C5H5) reacted with As4S4 to give [Cp2W(H)(η1-As5S2)] (6). The structures were determined by X-ray crystallography. Compounds 1 and 2 are dimers in which two Cp′M units are symmetrically bridged by a μ,η2:2-AsS3 ligand, a sulfide ligand and a heteroallylic μ,η2:2-AsS2 ligand. The structure of 6 belongs to the type of bent metallocenes in which tungsten is surrounded tetrahedrally by two Cp ligands, a crystallographically found hydride atom and the new As5S2 cage. The reaction of 1 with W(CO)5THF gave [Cp′2Nb2As2S6·W(CO)5] (3) and [Cp′2Nb2As2S6W(CO)3·W…
Electron-Sponge Behavior, Reactivity and Electronic Structures of Cobalt-Centered Cubic Co9Te6(CO)8 Clusters
Extended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]–/[3]2–/[3]3–/[3]4–/[3]5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]– containing salts…