Dataset Information

Structural diversity of mixed polypnictogen complexes: dicationic E₂E'₂ (E = E' = P, As, Sb, Bi) chains, cycles and cages stabilized by transition metals.

ABSTRACT: The reactivity of the tetrahedral dipnictogen complexes [{CpMo(CO)₂}₂(μ,η²:η²-EE')] (E, E' = P, As, Sb, Bi; "Mo₂EE'") towards different one-electron oxidation agents is reported. Oxidation with [Thia][TEF] (Thia⁺ = C₁₂H₈S₂ ⁺; TEF^- = Al{OC(CF₃)₃}₄ ^-) leads to the selective formation of the radical monocations [Mo₂EE']˙⁺, which immediately dimerize to the unprecedented dicationic E₂E'₂ ligand complexes [{CpMo(CO)₂}₄(μ₄,η²:η²:η²:η²-E'EEE')]²⁺ via E-E bond formation. Single crystal X-ray diffraction revealed that, in the case of Mo₂PAs and Mo₂PSb, P-P bond formation occurs yielding zigzag E₂P₂ (E = As (1), Sb (2)) chains, whereas Mo₂SbBi forms a Sb₂Bi₂ (5) cage, Mo₂AsSb an unprecedented As₂Sb₂ unit representing an intermediate stage between a chain- and a cage-type structure, and Mo₂AsBi a novel planar As₂Bi₂ (4a) cycle. Therefore, 1-5 bear the first substituent-free, dicationic hetero-E₄ ligands, stabilized by transition metal fragments. Furthermore, in the case of Mo₂AsSb, the exchange of the counterion causes changes in the molecular structure yielding an unusual, cyclic As₂Sb₂ ligand. The experimental results are corroborated by DFT calculations.

SUBMITTER: Dutsch L

PROVIDER: S-EPMC8580054 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Structural diversity of mixed polypnictogen complexes: dicationic E2E'2 (E ≠ E' = P, As, Sb, Bi) chains, cycles and cages stabilized by transition metals.

Dütsch Luis L Riesinger Christoph C Balázs Gábor G Seidl Michael M Scheer Manfred M

Chemical science 20211014 43

The reactivity of the tetrahedral dipnictogen complexes [{CpMo(CO)2}2(μ,η2:η2-EE')] (E, E' = P, As, Sb, Bi; "Mo2EE'") towards different one-electron oxidation agents is reported. Oxidation with [Thia][TEF] (Thia+ = C12H8S2 +; TEF- = Al{OC(CF3)3}4 -) leads to the selective formation of the radical monocations [Mo2EE' ...[more]

PMID: 34881004

Similar Datasets

Project description:The realization of stable monolayers from 2D van der Waals (vdW) solids has fueled the search for exfoliable crystals with even lower dimensionalities. To this end, 1D and quasi-1D (q-1D) vdW crystals comprising weakly bound subnanometer-thick chains have been discovered and demonstrated to exhibit nascent physics in the bulk. Although established micromechanical and liquid-phase exfoliation methods have been applied to access single isolated chains from bulk crystals, interchain vdW interactions with nonequivalent strengths have greatly hindered the ability to achieve uniform single isolated chains. Here, we report that encapsulation of the model q-1D vdW crystal, Sb2Se3, within single-walled carbon nanotubes (CNTs) circumvents the relatively stronger c-axis vdW interactions between the chains and allows for the isolation of single chains with structural integrity. High-resolution transmission electron microscopy and selected area electron diffraction studies of the Sb2Se3@CNT heterostructure revealed that the structure of the [Sb4Se6]n chain is preserved, enabling us to systematically probe the size-dependent properties of Sb2Se3 from the bulk down to a single chain. We show that ensembles of the [Sb4Se6]n chains within CNTs display Raman confinement effects and an emergent band-like absorption onset around 600 nm, suggesting a strong blue shift of the near-infrared band gap of Sb2Se3 into the visible range upon encapsulation. First-principles density functional theory calculations further provided qualitative insight into the structures and interactions that could manifest in the Sb2Se3@CNT heterostructure. Spatial visualization of the calculated electron density difference map of the heterostructure indicated a minimal degree of electron donation from the host CNT to the guest [Sb4Se6]n chain. Altogether, this model system demonstrates that 1D and q-1D vdW crystals with strongly anisotropic vdW interactions can be precisely studied by encapsulation within CNTs with suitable diameters, thereby opening opportunities in understanding dimension-dependent properties of a plethora of emergent vdW solids at or approaching the subnanometer regime.

Dataset Information

Structural diversity of mixed polypnictogen complexes: dicationic E₂E'₂ (E = E' = P, As, Sb, Bi) chains, cycles and cages stabilized by transition metals.

Publications

Structural diversity of mixed polypnictogen complexes: dicationic E<sub>2</sub>E'<sub>2</sub> (E ≠ E' = P, As, Sb, Bi) chains, cycles and cages stabilized by transition metals.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Dataset Information

Structural diversity of mixed polypnictogen complexes: dicationic E2E'2 (E = E' = P, As, Sb, Bi) chains, cycles and cages stabilized by transition metals.

Publications

Structural diversity of mixed polypnictogen complexes: dicationic E<sub>2</sub>E'<sub>2</sub> (E ≠ E' = P, As, Sb, Bi) chains, cycles and cages stabilized by transition metals.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Structural diversity of mixed polypnictogen complexes: dicationic E₂E'₂ (E = E' = P, As, Sb, Bi) chains, cycles and cages stabilized by transition metals.