Browse
Submit Data
Databases
API
Help

Dataset Information

16 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules.

ABSTRACT: A range of reasons has been suggested for why many low-coordinate complexes across the periodic table exhibit a geometry that is bent, rather a higher symmetry that would best separate the ligands. The dominating reason or reasons are still debated. Here we show that two pyramidal UX₃ molecules, in which X is a bulky anionic ligand, show opposite behaviour upon pressurisation in the solid state. UN″₃ (UN3, N″ = N(SiMe₃)₂) increases in pyramidalization between ambient pressure and 4.08 GPa, while U(SAr)₃ (US3, SAr = S-C₆H₂-^tBu₃-2,4,6) undergoes pressure-induced planarization. This capacity for planarization enables the use of X-ray structural and computational analyses to explore the four hypotheses normally put forward for this pyramidalization. The pyramidality of UN3, which increases with pressure, is favoured by increased dipole and reduction in molecular volume, the two factors outweighing the slight increase in metal-ligand agostic interactions that would be formed if it was planar. The ambient pressure pyramidal geometry of US3 is favoured by the induced dipole moment and agostic bond formation but these are weaker drivers than in UN3; the pressure-induced planarization of US3 is promoted by the lower molecular volume of US3 when it is planar compared to when it is pyramidal.

SUBMITTER: Price AN

PROVIDER: S-EPMC9262880 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Solid-State Structure of Tris-Cyclopentadienide Uranium(III) and Plutonium(III).

Project description:The organometallic tris-cyclopentadienide actinide(III) (AnCp3 ) complexes were first reported about 50 years ago. However, up until now, only the NpCp3 solid state structure has been studied. Here we report on the solid state structures of UCp3 and PuCp3 which are isostructural to the Np analogue. The structural models are supported by theoretical calculations and compared to their lanthanide analogues. The observed trends in changes of bond lengths might be indicator for an increased covalency in the bonding in the tris-cyclopentadienide actinide(III) complexes (AnCp3 ) compared to their lanthanide homologues.

| S-EPMC5861669 | biostudies-literature

Tris[dimethyl (benzoyl-amido)-phosphato-?(2) O,O'](1,10-phenanthroline-?(2) N,N')neodymium(III).

Project description:In both independent mol-ecules of the title compound, [Nd(C9H11NO4P)3(C12H8N2)], the Nd(III) atom is coordinated by six O atoms belonging to three phosphoryl ligands and two N atoms of 1,10-phenanthroline in a dodeca-hedral geometry. In the phosphoryl ligands, the benzene rings are twisted with respect to the planes of the sp(2)-hybridized C atoms of the chelate rings by 12.1?(1)-24.7?(1)°.

| S-EPMC3588435 | biostudies-literature

Nickel(II) uranium(IV) tris-ulfide.

Project description:Crystals of NiUS3 were obtained from the reaction of the elements Ni, U, S, and of GeI2 in a CsCl flux at 1173?K. Nickel(II) uranium(IV) tris-ulfide, NiUS3, has ortho-rhom-bic (Pnma) symmetry and crystallizes in the GdFeO3 structure type. The compound has a perovskite ABQ 3-like structure, with U occupying the inter-stitial sites of a NiS6 framework. The U atoms are coordinated by eight S atoms in a distorted bicapped trigonal-prismatic arrangement. The Ni atoms are coordinated by six S atoms in a slightly distorted octa-hedral arrangement. The asymmetric unit comprises one U site (site symmetry .m.), one Ni site (-1), and two S sites (1 and .m.).

| S-EPMC3914034 | biostudies-literature

Computational DFT data related to the redox behaviour of tris(?-diketonato)ruthenium(III) compounds.

Project description:The data presented in this paper are related to the research article titled "Redox Behaviour of [Ru(?-diketonato)3] Compounds" [1]. This paper presents structural and energy data obtained from the density functional theory (DFT) computations. The energy data is related to experimentally obtained redox potential values. Various relationships are presented for the RuIII/II and RuIII/IV redox couples, involving both their experimental redox data as well as DFT calculated data, such as frontier orbital energies (E HOMO and E LUMO) and calculated Mulliken electronegativity values.

| S-EPMC7206207 | biostudies-literature

Tris(ethyl-enediamine-?N,N')cobalt(III) aqua-tris-(oxalato-?O,O)indate(III).

Project description:In the cation of the title compound, [Co(C(2)H(8)N(2))(3)][In(C(2)O(4))(3)(H(2)O)], the Co(III) atom is coordinated by six N atoms from three ethyl-enediamine mol-ecules. The Co(III)-N bond lengths lie in the range 1.956?(4)-1.986?(4)?Å. In the anion, the In(III) atom is seven-coordinated by six O atoms from three oxalate ligands and by a water mol-ecule. The cations and anions are linked by extensive O-H?O and N-H?O hydrogen bonds, forming a supermolecular network.

| S-EPMC3254329 | biostudies-literature

Tris(ethyl-enediamine)-cobalt(III) diformatodioxalatoindate(III) dihydrate.

Project description:In the cation of the title compound, [Co(C(2)H(8)N(2))(3)][In(C(2)O(4))(2)(CHO(2))(2)]·2H(2)O, the Co-N bond lengths lie in the range 1.960?(5)-1.997?(5)?Å. In the anion, the In(III) atom is coordin-ated by four O atoms from two oxalato ligands and two O atoms from two formato ligands in a distorted octa-hedral geometry. Inter-molecular O-H?O and N-H?O hydrogen bonds form an extensive hydrogen-bonding network, which link the cations, anions and water mol-ecules into three-dimensional structure.

| S-EPMC3089116 | biostudies-literature

Tris(2,2'-bipyridine-?N,N')cobalt(III) tris-(oxalato-?O,O)ferrate(III) mono-hydrate.

Project description:The title compound, [Co(C(10)H(8)N(2))(3)][Fe(C(2)O(4))(3)]·H(2)O, con-sists of two discrete tris-(chelate) metal ions (Co(III)N(6) and Fe(III)O(6) chromophores) and a water mol-ecule. The structure is highly symmetrical; the Co(III) and Fe(III) ions occupy positions with site symmetry 3.2. The coordination polyhedra of the metal atoms have a nearly octa-hedral geometry with noticeable trigonal distortions. The Co-N and Fe-O bond lengths are equal by symmetry, viz. 1.981?(2) and 1.998?(4)?Å, respectively. The cations and anions are arranged alternately along their threefold rotation axes parallel to [001], forming chains that are packed in a hexa-gonal manner. The water mol-ecules occupy voids between the chains. The crystal under investigation was an inversion twin.

| S-EPMC3297208 | biostudies-literature

Transient Covalency in Molten Uranium(III) Chloride.

Project description:Uranium is arguably the most essential element in the actinide series, serving as a crucial component of nuclear fuels. While U is recognized for engaging the 5f orbitals in chemical bonds under normal conditions, little is known about its coordination chemistry and the nature of bonding interactions at extreme conditions of high temperature. Here we report experimental and computational evidence for the shrinkage of the average U-ligand distance in UCl3 upon the solid-to-molten phase transition, leading to the formation of a significant fraction of short, transient U-Cl bonds with the enhanced involvement of U 5f valence orbitals. These findings reveal that extreme temperatures create an unusual heterogeneous bonding environment around U(III) with distinct inner- and outer-coordination subshells.

| S-EPMC11311222 | biostudies-literature

Tris(thio-cyanato-?N)tris-(triphenyl-phosphine oxide-?O)terbium(III).

Project description:The title compound, [Tb(NCS)3(C18H15OP)3], contains a six-coordinate Tb(II) cation surrounded by three O-bound triphenyl-phosphine oxide ligands and three N-bound thio-cyanate ligands, each in a fac arrangement. There are two crystallographically unique Tb(III) atoms in the asymmetric unit. One Tb(III) atom resides on a threefold rotation axis, while the other has no imposed crystallographic symmetry. The thio-cyanate ligands are bound through N atoms, illustrating the hard-hard bonding principles of metal complex chemistry.

| S-EPMC3588775 | biostudies-literature

Hexaaqua-aluminium(III) tris-(methane-sulfonate).

Project description:The title compound, [Al(H(2)O)(6)](CH(3)SO(3))(3) (common name: aluminium methane-sulfonate hexa-hydrate), was crystallized from an aqueous solution prepared by the precipitation reaction of aluminium sulfate and barium methane-sulfonate. Its crystal structure is the first of the boron group methane-sulfonates to be determined. The characteristic building block is a centrosymmetric unit containing two hexa-aqua-aluminium cations that are connected to each other by two O atoms of the -SO(3) groups in an O-H?O?H-O sequence. Further O-H?O hydrogen bonding links these blocks in orthogonal directions - along [010] forming a double chain array, along [10-1] forming a layered arrangement of parallel chains and along [101] forming a three-dimensional network. As indicated by the O?O distances of 2.600?(3)-2.715?(3)?Å, the hydrogen bonds are from medium-strong to strong. A further structural feature is the arrangement of two and four methyl groups, respectively, establishing 'hydro-phobic islands' of different size, all positioned in a layer-like region perpendicular to [101]. The only other building block within this region is one of the -SO(3) groups giving a local connection between the hydro-philic structural regions on both sides of the 'hydro-phobic' one. Thermal analysis indicates that a stepwise dehydration process starts at about 413?K and proceeds via the respective penta- and dihydrate until the compound completely decomposes at about 688?K.

| S-EPMC3414175 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data