Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Highly Coordinated Heteronuclear Calcium-Iron Carbonyl Cation Complexes [CaFe(CO)_n ]⁺ (n=5-12) with d-d Bonding.

ABSTRACT: Heteronuclear calcium-iron carbonyl cation complexes in the form of [CaFe(CO)_n ]⁺ (n=5-12) are produced in the gas phase. Infrared photodissociation spectroscopy in conjunction with quantum chemical calculations confirm that the n=10 complex is the coordination saturated ion where a Fe(CO)₄ fragment is bonded with a Ca(CO)₆ fragment through two side-on bridging carbonyl ligands. Bonding analysis indicates that it is best described by the bonding interactions between a [Ca(CO)₆ ]²⁺ dication and an [Fe(CO)₄ ]^- anion forming a Fe→Ca d-d dative bond in the [(CO)₆ Ca-Fe(CO)₄ ]⁺ structure, which enriches the pool of experimentally observed complexes of calcium that mimic transition metal compounds. The molecule is the first example of a heteronuclear carbonyl complex featuring a d-d bond between calcium and a transition metal.

SUBMITTER: Jin X

PROVIDER: S-EPMC8251804 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)5 }2 ]+ (M=Cu, Ag, Au).

Project description:Syntheses of the copper and gold complexes [Cu{Fe(CO)5 }2 ][SbF6 ] and [Au{Fe(CO)5 }2 ][HOB{3,5-(CF3 )2 C6 H3 }3 ] containing the homoleptic carbonyl cations [M{Fe(CO)5 }2 ]+ (M=Cu, Au) are reported. Structural data of the rare, trimetallic Cu2 Fe, Ag2 Fe and Au2 Fe complexes [Cu{Fe(CO)5 }2 ][SbF6 ], [Ag{Fe(CO)5 }2 ][SbF6 ] and [Au{Fe(CO)5 }2 ][HOB{3,5-(CF3 )2 C6 H3 }3 ] are also given. The silver and gold cations [M{Fe(CO)5 }2 ]+ (M=Ag, Au) possess a nearly linear Fe-M-Fe' moiety but the Fe-Cu-Fe' in [Cu{Fe(CO)5 }2 ][SbF6 ] exhibits a significant bending angle of 147° due to the strong interaction with the [SbF6 ]- anion. The Fe(CO)5 ligands adopt a distorted square-pyramidal geometry in the cations [M{Fe(CO)5 }2 ]+ , with the basal CO groups inclined towards M. The geometry optimization with DFT methods of the cations [M{Fe(CO)5 }2 ]+ (M=Cu, Ag, Au) gives equilibrium structures with linear Fe-M-Fe' fragments and D2 symmetry for the copper and silver cations and D4d symmetry for the gold cation. There is nearly free rotation of the Fe(CO)5 ligands around the Fe-M-Fe' axis. The calculated bond dissociation energies for the loss of both Fe(CO)5 ligands from the cations [M{Fe(CO)5 }2 ]+ show the order M=Au (De =137.2 kcal mol-1 )>Cu (De =109.0 kcal mol-1 )>Ag (De =92.4 kcal mol-1 ). The QTAIM analysis shows bond paths and bond critical points for the M-Fe linkage but not between M and the CO ligands. The EDA-NOCV calculations suggest that the [Fe(CO)5 ]→M+ ←[Fe(CO)5 ] donation is significantly stronger than the [Fe(CO)5 ]←M+ →[Fe(CO)5 ] backdonation. Inspection of the pairwise orbital interactions identifies four contributions for the charge donation of the Fe(CO)5 ligands into the vacant (n)s and (n)p AOs of M+ and five components for the backdonation from the occupied (n-1)d AOs of M+ into vacant ligand orbitals.

| S-EPMC8252735 | biostudies-literature

Formation and Reactivity of a Hexahydridosilicate [SiH6 ]2- Coordinated by a Macrocycle-Supported Strontium Cation.

Project description:The cationic benzyl complex [(Me4 TACD)Sr(CH2 Ph)][A] (Me4 TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C6 H3 -3,5-Me2 )4 ) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me4 TACD)2 Sr2 (thf)4 (μ-κ3 : κ3 -SiH6 )][A]2 (3 a). Rapid phenyl exchange between phenylsilane molecules is assumed to generate monosilane SiH4 that is trapped by two strontium hydride cations [(Me4 TACD)SrH(thf)x ]+ . Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me4 TACD)Sr(SiH3 )(thf)2 ][A], with release of H2 . Upon reaction with a weak Brønsted acid, CO2 , and 1,3,5,7-cyclooctatetraene SiH4 was released. The reaction of a 1 : 2 mixture of cationic benzyl and neutral dibenzyl complex with phenylsilane gave the trinuclear silanide complex [(Me4 TACD)3 Sr3 (μ2 -H)3 (μ3 -SiH3 )2 ][A], while n OctSiH3 led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me4 TACD)3 Sr3 (μ2 -H)3 (μ3 -SiH5 n Oct)][A].

| S-EPMC9303417 | biostudies-literature

Designing a super broadband near infrared material Mg3Y2Ge3O12:Cr3+ using cation inversion for future light sources.

Project description:A series of broad emission band near infrared materials Mg3Y2Ge3O12:Cr3+ (650-1200 nm) was prepared based on cation inversion. For trivalent chromium ions (Cr3+), garnet structural components can provide conditions for the occurrence of cation inversion. With an increase in Cr3+ concentration, the Mg2+ and Ge4+ cations are inverted to ensure valence equilibrium, which was explained by recording the low temperature spectrum of the structure and carrying out structural refinement. As a result, this structure provides a new luminescent center [GeO6] for Cr3+, leading to a secondary enhancement in emission intensity. The wavelength of the main peak was found to move from 771 to 811 nm, and the full width at half maximum (FWHM) was broadened from 180 to 226 nm. The lattice occupation, luminescence mechanism and the reasons behind the red-shift and broadening of the spectra were studied in detail. By analyzing the crystallinity and particle size distributions of the samples, as well as the Cr3+ ion energy level shift, it was determined that cation inversion is an effective method that can be used to tune the luminescence performance. Meanwhile, a super broad near infrared light emitting diode (LED) with a FWHM of 260 nm was obtained by combining a GaN chip with MYG:0.40Cr3+.

| S-EPMC9053909 | biostudies-literature

Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12).

Project description:The hexagonal mixed-anion solid solution Na2(CB9H10)(CB11H12) shows the highest room-temperature ionic conductivity among all known Na-ion conductors. To study the dynamical properties of this compound, we have measured the 1H and 23Na nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates in Na2(CB9H10)(CB11H12) over the temperature range of 80-435 K. It is found that the diffusive motion of Na+ ions can be described in terms of two jump processes: the fast localized motion within the pairs of tetrahedral interstitial sites of the hexagonal close-packed lattice formed by large anions and the slower jump process via octahedral sites leading to long-range diffusion. Below 350 K, the slower Na+ jump process is characterized by the activation energy of 353(11) meV. Although Na+ mobility in Na2(CB9H10)(CB11H12) found from our NMR experiments is higher than in other ionic conductors, it appears to be an order-of-magnitude lower than that expected on the basis of the conductivity measurements. This result suggests that the complex diffusion mechanism and/or correlations between Na+ jumps should be taken into account. The measured 1H spin-lattice relaxation rates for Na2(CB9H10)(CB11H12) are consistent with a coexistence of at least two anion reorientational jump processes occurring at different frequency scales. Near room temperature, both reorientational processes are found to be faster than the Na+ jump process responsible for the long-range diffusion.

| S-EPMC11187972 | biostudies-literature

Stabilization of hydrated AcIII cation: the role of superatom states in actinium-water bonding.

Project description:225Ac-based radiopharmaceuticals have the potential to become invaluable in designated cancer therapy. However, the limited understanding of the solution chemistry and bonding properties of actinium has hindered the development of existing and emerging targeted radiotherapeutics, which also poses a significant challenge in the discovery of new agents. Herein, we report the geometric and electronic structural properties of hydrated AcIII cations in the [AcIII(H2O) n ]3+ (n = 4-11) complexes in aqueous solution and gas-phase using density functional theory. We found that nine water molecules coordinated to the AcIII cation is the most stable complex due to an enhanced hydration Gibbs free energy. This complex adopts a closed-shell 18-electron configuration (1S 21P 61D 10) of a superatom state, which indicates a non-negligible covalent character and involves H2O → AcIII σ donation interaction between s-/p-/d-type atomic orbitals of the Ac atom and 2p atomic orbitals of the O atoms. Furthermore, potentially existing 10-coordinated complexes need to overcome an energy barrier (>0.10 eV) caused by hydrogen bonding to convert to 9-coordination. These results imply the importance of superatom states in actinide chemistry generally, and specifically in AcIII solution chemistry, and highlight the conversion mechanism between different coordination numbers.

| S-EPMC8179294 | biostudies-literature

The Impact of Cr3+ Doping on Temperature Sensitivity Modulation in Cr3+ Doped and Cr3+, Nd3+ Co-doped Y3Al5O12, Y3Al2Ga3O12, and Y3Ga5O12 Nanothermometers.

Project description:A new approach to enhance the sensitivity of transition metal ion based nanocrystalline luminescent thermometer is presented. It was shown that the increase of Cr3+ concentration in three types of garnet host namely Y3Al5O12, Y3Ga5O12, and Y3Al2Ga3O12 allows for significant enhancement of their performance in non-contact thermometry. This phenomenon is related to the weakening of the crystal field strength due to enlargement of average Cr3+-O2- distance at higher Cr3+ concentrations. By increasing Cr3+ concentration from 0.6 to 30%, the sensitivity increased by over one order of magnitude from S = 0.2%/°C to S = 2.2%/°C at 9°C in Y3Al2Ga3O12 nanocrystals. Moreover, it was found that due to the Cr3+ ? Nd3+ energy transfer in the Cr3+, Nd3+ co-doped system, the usable Cr3+ concentration, for which its emission can be detected, is limited to 10% while the sensitivity at -50°C was doubled (from 1.3%/°C for Y3Al2Ga3O12:10%Cr3+ to 2.2%/°C Y3Al2Ga3O12:10%Cr3+, 1%Nd3+ nanocrystals).

| S-EPMC6157326 | biostudies-literature

A Dynamic Proton Bond: MH+·H2O ⇌ M·H3O+ Interconversion in Loosely Coordinated Environments.

Project description:The interaction of organic molecules with oxonium cations within their solvation shell may lead to the emergence of dynamic supramolecular structures with recurrently changing host-guest chemical identity. We illustrate this phenomenon in benchmark proton-bonded complexes of water with polyether macrocyles. Despite the smaller proton affinity of water versus the ether group, water in fact retains the proton in the form of H3O+, with increasing stability as the coordination number increases. Hindrance in many-fold coordination induces dynamic reversible (ether)·H3O+ ⇌ (etherH+)·H2O interconversion. We perform infrared action ion spectroscopy over a broad spectral range to expose the vibrational signatures of the loose proton bonding in these systems. Remarkably, characteristic bands for the two limiting proton bonding configurations are observed in the experimental vibrational spectra, superimposed onto diffuse bands associated with proton delocalization. These features cannot be described by static equilibrium structures but are accurately modeled within the framework of ab initio molecular dynamics.

| S-EPMC9923742 | biostudies-literature

Chemical Bonding in Silicon Carbonyl Complexes.

Project description:Although silylene-carbonyl complexes are known for decades, only recently isolable examples have been accomplished. In this work, the bonding situation is re-evaluated to explain the origins of their remarkable stability within the Kohn-Sham molecular orbital theory framework. It is shown that the chemical bond can be understood as CO interaction with the silylene via a donor-acceptor interaction: a σ-donation from the σCO into the empty p-orbital of silicon, and a π-back donation from the sp2 lone pair of silicon into the π*CO antibonding orbitals. Notably, it was established that the driving force behind the surprisingly stable Si-CO compounds, however, is another π-back donation from a perpendicular bonding R-Si σ-orbital into the π*CO antibonding orbitals. Consequently, the pyramidalization of the central silicon atom cannot be associated with the strength of the π-back donation, in sharp contrast to the established chemical bonding model. Considering this additional bonding interaction not only shed light on the bonding situation, but is also an indispensable key for broadening the scope of silylene-carbonyl chemistry.

| S-EPMC8360033 | biostudies-literature

Templation and Concentration Drive Conversion Between a FeII12L12 Pseudoicosahedron, a FeII4L4 Tetrahedron, and a FeII2L3 Helicate.

Project description:We report the construction of three structurally distinct self-assembled architectures: FeII12L12 pseudoicosahedron 1, FeII2L3 helicate 2, and FeII4L4 tetrahedron 3, formed from a single triazatriangulenium subcomponent A under different reaction conditions. Pseudoicosahedral capsule 1 is the largest formed through subcomponent self-assembly to date, with an outer-sphere diameter of 5.4 nm and a cavity volume of 15 nm3. The outcome of self-assembly depended upon concentration, where the formation of pseudoicosahedron 1 was favored at higher concentrations, while helicate 2 exclusively formed at lower concentrations. The conversion of pseudoicosahedron 1 or helicate 2 into tetrahedron 3 occurred following the addition of a CB11H12- or B12F122- template.

| S-EPMC9097479 | biostudies-literature

Reactivity of a coordinated inorganic acetylene unit, HBNH, and the azidoborane cation [HB(N3)].

Project description:A donor-acceptor complex of HBNH was prepared via thermolysis of a carbene-stabilized azidoborane. The reactivity of the fundamentally important HBNH unit (inorganic alkyne analogue) was explored in detail, including attempts to convert this species and related hydrido(azido)borane cations into molecular complexes of BN. This work provides added impetus for the development of molecular precursors that can release bulk boron nitride (a desirable insulator and thermal conductor) under mild conditions, and from solution.

| S-EPMC5365008 | biostudies-literature