0000000000364735
AUTHOR
Manfred Zabel
Isomerism and Ligand Rearrangement within the cyclo-P2S3 Middle Deck in Dimolybdenum Triple-Decker Complexes
The molecular structure of [Cp*2Mo2P2S3] (1; Cp* = η5-C5Me5) has been reinvestigated. In DFT studies a series of various positional isomers A−E have been calculated for the model complex [(C5H5)2Mo2P2S3]. The energetically favored isomer [Cp*2Mo2(μ,η2:2-PS)2(μ-S)] (1B) reacts with W(CO)5THF to give [Cp*2Mo2P2S3·W(CO)5] (2). X-ray diffraction analysis of 2 confirms the presence of two η2:2-PS dumbbells and one singly bridging sulfur ligand, the W(CO)5 fragment being coordinated at one of the P atoms. Arrangement B is also found in the structure of the diadduct [Cp°2Mo2P2S3{W(CO)5}2] (3; Cp° = t-BuMe2C5H2), which is more stable than its Cp* analogue. 31P solid-state MAS NMR spectroscopic stud…
Chemistry of transition-metal clusters with mixed Sb/S ligands: evidence for a terminal Sb=S double bond in Cp*3Rh3Sb2S5 (Cp* = C5Me5).
The reaction of [Cp 2 *Rh 2 Cl 4 ] (Cp* = C 5 Me 5 ) with a slight excess of K 3 SbS 3 in boiling THF gave the neutral clusters [Cp* 4 Rh 4 S 5 ] (1), [Cp* 3 Rh 3 Sb 2 S 5 ] (2), and after salt metathesis [Cp* 3 Rh 3 SbS n ]PF 6 (3; n = 5 and 6). The structures of 1-3 are heterocubane clusters with Cp*Rh, S, and Sb vertices but with sulfur inserted into one (1 and 2) or two (3) edges. X-ray diffraction analysis of 2 additionally reveals a very short Sb-S distance of 2.297(1) A within the novel μ 3 -Sb 2 S 4 ligand. Density functional theory calculation of the model compounds [SSbS] 3 - , [HSSbS] 2 - , and [HSSbH 2 S] 0 provided strong evidence for the existence of a stable terminal Sb=S dou…
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.
Synthesis, reactivity and structures of ruthenium carbonyl clusters with telluride and hydride ligands
The reaction of [Cp* 2 Nb(Te 2 H)] ( 1 ) (Cp*=C 5 Me 5 ) with [Ru 3 (CO) 12 ] in boiling toluene gave [Ru 3 (μ 2 -H) 2 (CO) 9 (μ 3 -Te)] ( 2 ), [Ru 6 (μ 3 -H)(CO) 15 (μ 3 -Te) 3 ][Cp* 2 Nb(CO) 2 ] ( 3 ) and [Ru 5 (μ 2 -H)(CO) 14 (μ 4 -Te)][Cp* 2 Nb(CO) 2 ] ( 4 ) along with already known [Ru 4 (CO) 11 (μ 4 -Te) 2 ] ( 5 ). Complexes 2 – 4 were analytically and spectroscopically characterized and X-ray diffraction analyses of 3 and 4 were carried out. The anion of 3 is built up of a triangular hexametallic core of C 3 v symmetry, in which the central Ru 3 triangle, being bridged by a μ 3 -H ligand, is composed of three corner-linked Ru 3 Te tetrahedra. The main structural feature of the anion …
Mu,eta2:2-SbS: an antimony-containing heterodiatomic ligand from group 15 and 16 elements.
Electron-Sponge Behavior and Electronic Structures in Cobalt-Centered Pentagonal Prismatic Co11Te7(CO)10 and Co11Te5(CO)15 Cluster Anions
The novel cluster anion [Co11Te5(CO)15]- ([3]-) has been isolated and structurally characterized as part of the salt [Cp*2Nb(CO)2][3] (Cp* = C5Me5). The cobalt-centered Co10 pentagonal prism is surrounded by a shell of two μ5-Te, three μ4-Te ligands, and 15 CO groups in terminal, symmetrical, and σ-semibridging bonding modes. The hybrid carbonyl-telluride character of the ligand shell is reflected in the solid state by a one-dimensional assembly of polyhedral prisms along a backbone of [Cp*2Nb(CO)2]+ cations. Electrochemical studies reveal the presence of four redox couples of [3]n (n = −1 to −5). The electronic structures of various metal-centered and empty pentagonal-prismatic (PP) M10 cl…
Preparative and Electrochemical Investigations on the Electron Sponge Behavior of Cobalt Telluride Clusters: CO Substitution in[Co11Te7(CO)10]n− Ions (n=1, 2) by PMe2Ph and Crystal Structure of[Co11Te7(CO)5(PMe2Ph)5]
The reaction of the cluster salts [Cp* 2 Nb(CO) 2 ] n [Co 1 1 Te 7 (CO) 1 0 ] (Cp* = C 5 Me 5 ; n = 1, 2) with excess PMe 2 Ph gave the neutral, dark brown clusters [Co 1 1 Te 7 (CO) 6 (PMe 2 Ph) 4 ] (5) and [Co 1 1 Te 7 (CO) 5 (PMe 2 Ph) 5 ] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X+ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co 1 1 Te 7 ] core, but with a ligand sphere composed of five CO and five PMe 2 Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of C…
Syntheses, Properties and Structures of [{(C 5 Me 5 ) 2 Nb} 2 NiTe 4 ] and [( t BuC 5 H 4 Nb) 2 Ni 5 Te 7 (Ph 2 PCH 2 PPh 2 ) 2 ]: The Quest for Tetratelluronickelate Clusters
The reaction of [Ni(COD) 2 ] with [Cp* 2 NbTe 2 H] (1; Cp * = η-C 5 Me 5 ) in the presence of Ph 2 PCH 2 PPh 2 (dppm) in boiling toluene gives black-violet [(Cp * 2 Nb) 2 NiTe 4 ] (3). If [Cp' 2 NbTe 2 H] (2; Cp' = tBuC 5 H 4 ) is used under similar conditions dark-brown [(Cp'Nb)2Ni5Te7(dppm)2] (4) is formed. The structures of 3 and 4 have been determined crystallographically. Complex 3 contains a severely distorted NiTe 4 tetrahedron to which two niobocene groups are coordinated. Density functional analysis of the electronic structure of the NiTe 4 building block shows that it is best described as an [Ni(η 2 -Te 2 ) 2 ] 2- fragment. The structure of 4 reveals the presence of two Ni 5 and T…
Bis(η-tert-butylcyclopentadienyl)hydridoniobium Ditelluride, a Convenient Reagent for the Synthesis of Polynuclear Metal Telluride Complexes
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…
Metal Telluride Clusters Composed of Niobocene Carbonyl, Telluride, and Cobalt Carbonyl Units: Syntheses, Structures, and Reactivity
Abstract: The reaction of [Cp#2NbTe2H] (1#; Cp# = Cp* (C5Me5) or Cp(x) (C5Me4Et)) with two equivalents of [Co2(CO)8] gives a series of cobalt carbonyl telluride clusters that contain different types of niobocene carbonyl fragments. At 0 degrees C, [Cp#2NbTe2CO3(CO)7] (2#) and [Co4Te2(CO)10] (3) are formed which disappear at higher temperatures: in boiling toluene a mixture of [cat2][Co9Te6(CO)8] (5#) (cat= [Cp#2Nb(CO)2]+) and [cat2][Co11Te7(CO)10] (6#) is formed along with [cat][Co(CO)4] (4#). Complexes 6# transform into [cat][Co11Te7(CO)10] (7#) upon interaction with HPF6 or wet SiO2. The molecular structures of 2(Cp(x)), 4(Cp(x)), 5(Cp*), 6(Cp*) and 7(Cp*) have been determined by X-ray cr…
A New Building Block for Organometallic–Inorganic Hybrid Polymers: The Mixed Group 15/16 Element Ligand Complex [Cp* 2 Mo 2 (μ,η 2:2 ‐PSe) 2 (μ‐Se)] (Cp* = C 5 Me 5 )
The synthesis and spectroscopic characterization of [Cp*2Mo2P2Se3] (1; Cp* = C5Me5) and its use as a molecular building block in the formation of copper(I) halide polymers is described. The reaction of 1 in CH2Cl2 with 2 equiv. of CuBr and CuI in CH3CN under diffusion conditions gave [(Cp*2Mo2P2Se3)2(CuBr)2] (2) and [(Cp*2Mo2P2Se3)(CuX)3(CH3CN)]n (X = I; 3/4), respectively. The structure of 2 is distinguished by a central Cu2Br2 ring coordinated on each side by a tripledecker complex through one of its P atoms. A 2D network is formed by weak interactions between Se atoms of neighboring molecules. Compound [(Cp*2Mo2P2Se3)(CuI)3(CH3CN)]n exists in two isomeric forms 3 and 4. The crystal struc…
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…