Sandwich-like complexes based on "all-metal" (Al 4 2-) aromatic compounds

We report a new sandwich-like structure (Al4TiAl42-) based on the recently synthesized all-metal aromatic Al42- squares. This structure has two aromatic squares (-2 charged each) trapping a titanium +2 cation. These all-metal aromatic squares have been detected by various metallic counterions, with a global charge of -1. Thus, we have also characterized a similar sandwich-like structure interacting with one and two sodium atoms with global charges of -1 and 0. The properties of these compounds strongly support the idea that they may be formed by Al42- aromatic squares.     

Stabilization of an all-metal antiaromatic molecule (Al4Li4) using BH and C as caps

It has been reported by Pati et al. ( J. Am. Chem. Soc. 2005, 127, 3496) that coordination with a transition metal can stabilize the "antiaromatic", all-metal compound Al4Li4. Here, we report that it can also be stabilized by capping with a main group element like C and its isoelectronic species BH. Our calculations of binding energy, nuclear independent chemical shift, energy decomposition analysis, and molecular orbital analysis support the capping-induced stability, reduction of bond length alternation, and increase of aromaticity of these BH/C-capped Al4Li4 systems. The interaction between px and py orbitals of BH/C and the HOMO and LUMO of Al4Li4 is responsible for the stabilization. Our calculations suggest that capping can introduce fluxionality at room temperature.     

Stable transition metal complexes of an all-metal antiaromatic molecule (Al4Li4): role of complexations

We propose for the first time a few examples of stable transition metal complexes of an all-metal antiaromatic molecule Al4Li4. We demonstrate that these all-metal species can be stabilized by complexation with 3d transition metals very similar to their organic counterpart, C4H4. Complexation to transition metal ions reduces the frontier orbital energies and introduces aromatic charactersitics. We consider a series of such complexes: [eta4-(Al4Li4)-Fe(CO)3, eta2,sigma2-(Al4Li4)-Ni, and (Al4Li4)2Ni] and compare and contrast their energetics with their organometallic counterparts. Fragmentation energy, orbital correlation energy analysis, and the nucleus-independent chemical shift (NICS) values support the complexation-induced stabilities in these systems.     

Aromatic superclusters from all-metal aromatic and antiaromatic monomers, [Al4]2- and [Al4]4-

Calculations on the structures of dimers of all-metal aromatic and anti-aromatic molecules such as (Al4(2-)) and (Al4(4-)) reveal that, unlike their organic counterparts such as benzene and cyclobutadiene which form pi-stacked complexes, these molecules form new clusters with no reminiscence of the original units. These clusters have a very large binding energy and can be further stabilized through charge-balance by counterions and solvents.     

Sandwich complexes based on the "all-metal" Al4 2- aromatic ring

We report on novel sandwichlike structures [Al(4)MAl(4)](q-) (q=0-2 and M=Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W) based on the recently synthesized all-metal aromatic Al(4)(2-) square ring. The sandwichlike structures have two aromatic tetraaluminum square rings which trap a transition-metal cation from either the first, second, or third row. The stability of the anionic sandwichlike complexes towards electron detachment is discussed, and addition of alkali cations is found to stabilize the 2- charged complexes, preventing spontaneous electron detachment. Once the sandwichlike complexes are formed, the Al(4)(2-) square properties remain nearly unchanged; this fact strongly supports the hypothesis that in these complexes the Al(4)(2-) square rings remain aromatic.     

Bonding study in all-metal clusters containing Al4 units

The nature of the bonding of a series of gas-phase all-metal clusters containing the Al4 unit attached to an alkaline, alkaline earth, or transition metal is investigated at the DFT level using Mulliken, quantum theory of atoms in molecules (QTAIM), and Hirshfeld iterative (Hirshfeld-I) atomic partitionings. The characterization of ionic, covalent, and metallic bonds is done by means of charge polarization and multicenter electron delocalization. This Article uses for the first time Hirshfeld-I multicenter indices as well as Hirshfeld-I based atomic energy calculations. The QTAIM charges are in line with the electronegativity scale, whereas Hirshfeld-I calculations display deviations for transition metal clusters. The Mulliken charges fail to represent the charge polarization in alkaline metal clusters. The large ionic character of Li-Al and Na-Al bonds results in weak covalent bonds. On the contrary, scarcely ionic bonds (Be-Al, Cu-Al and Zn-Al) display stronger covalent bonds. These findings are in line with the topology of the electron density. The metallic character of these clusters is reflected in large 3-, 4- and 5-center electron delocalization, which is found for all the molecular fragments using the three atomic definitions. The previously reported magnetic inactivity (based on means of magnetic ring currents) of the pi system in the Al42- cluster contrasts with its large pi electron delocalization. However, it is shown that the different results not necessary contradict each other.     

Instability of the Al4(2-) "all-metal aromatic" ion and its implications

Al42 - is a prototype structural unit of a new class of "all-metal aromatic" molecules. Without stabilizing counterions this species is unstable with respect to electron autodetachment in the gas phase. We estimated the height of the repulsive Coulomb barrier to approximately 2.7 eV and calculated a lifetime of 9 fs. This is a short lifetime: The only way to study the isolated dianion experimentally is to use electron scattering techniques. Investigations of the validity of bound-state quantum chemical calculations on the isolated species show that the results suffer from significant admixture of continuum states to the bound-state wave function depending on the basis set. Calculations of molecular properties can therefore give essentially arbitrary results for this ill-defined system, as is demonstrated for the energy and nuclear magnetic shieldings. This substantiates that results from calculations on the isolated dianion should be approached with caution.     

Sandwich-like compounds based on the all-metal aromatic unit Al(4)2- and the main-group metals M (M=Li, Na, K, Be, Mg, Ca)

Inspired by the pioneering experimental characterisation of the all-metal aromatic unit Al(4)2- in the bimetallic molecules MAl4- (M=Li, Na, Cu) and by the very recent theoretical design of sandwich-type transition-metal complexes [Al4MAl4]q- (q=0-2; M=Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W), we used density functional theory (DFT) calculations (B3LYP/6-311+G(d) to design a series of novel non-transition-metal sandwich complexes based on the all-metal aromatic unit Al4(2-) and the main-group metals M (M=Li, Na, K, Be, Mg, Ca). The traditional homo-decked sandwich compounds [Al4MAl4]q- (without counterions) and (nM)q+[Al4MAl4]q- (with counterions M) (q=2-3, M=Li, Na, K, Be, Mg, Ca), although some of them are truly energy minima, have a much higher energy than many fused isomers. We thus concluded that it seems unlikely for Al4(2-) to sandwich the main-group metal atoms in the homo-decked sandwich form. Alternatively, we proposed a new type of sandwich complex, namely hetero-decked sandwich compounds [CpMAl4]q-, that are the ground-state structures for each M both with and without counterions. It was shown that with the rigid Cp- partner, the all-metal aromatic unit Al(4)2- might indeed act as a "superatom". These new types of all-metal aromatic unit-based sandwich complexes await future experimental verification.     

Li3Al(MoO4)3, a lyonsite molybdate

Trilithium aluminium trimolybdate(VI), Li₃Al(MoO₄)₃, has been grown as single crystals from α‐Al₂O₃ and MoO₃ in an Li₂MoO₄ flux at 998 K. This compound is an example of the well known lyonsite structure type, the general formula of which can be written as A₁₆B₁₂O₄₈. Because this structure can accomodate cationic mixing as well as cationic vacancies, a wide range of chemical compositions can adopt this structure type. This has led to instances in the literature where membership in the lyonsite family has been overlooked when assigning the structure type to novel compounds. In the title compound, there are two octahedral sites with substitutional disorder between Li⁺ and Al³⁺, as well as a trigonal prismatic site fully occupied by Li⁺. The (Li,Al)O₆ octahedra and LiO₆ trigonal prisms are linked to form hexagonal tunnels along the [100] axis. These polyhedra are connected by isolated MoO₄ tetrahedra. Infinite chains of face‐sharing (Li,Al)O₆ octahedra extend through the centers of the tunnels. A mixed Li/Al site, an Li, an Mo, and two O atoms are located on mirror planes.     

铁化合物-Al(i-Bu)3卤化物系催化剂的ESR研究

用ESR法研究了Fe(naph)2-Al(i-Bu)3-烯丙基氯和Fe(acac)3-Al(i-Bu)3-AlEt2Cl两个反应体系.以了解这类含铁催化剂的催化机理.结果表明,不管它们的起始铁化合物中的铁离子是II价还是III价,由它们和Al(i-Bu)3及卤化物反应组成的活性催化剂,其活性中心铁离子均是II价.这一结果为进一步确定铁系催化剂活性中心的结构提供了重要依据.     

Products of the addition of water molecules to Al3O3- clusters: structure, bonding, and electron binding energies in Al3O4H2-, Al3O5H4-, Al3O4H2, and Al3O5H4

Two stable products of reactions of water molecules with the Al3O3- cluster, Al3O4H2- and Al3O5H4-, are studied with electronic structure calculations. There are several minima with similar energies for both anions and the corresponding molecules. Dissociative absorption of a water molecule to produce an anionic cluster with hydroxide ions is thermodynamically favored over the formation of Al3O3-(H2O)n complexes. Vertical electron detachment energies of Al3O4H2- and Al3O5H4- calculated with ab initio electron propagator methods provide a quantitative interpretation of recent anion photoelectron spectra. Contrasts and similarities in these spectra may be explained in terms of the Dyson orbitals associated with each transition energy.     

Homocatenation of Aluminum: Alkane‐like Structures of Li2Al2H6 and Li3Al3H8

A new class of aluminum homocatenated compounds (Li_nAl_nH_2n+2) is proposed based on quantum chemical calculations. In these compounds, Al abstracts an electron from Li, becoming valence isoelectronic with C, Si, and Ge, thus mimicking respective structural features of Group 14 hydrides. Using the Coalescence Kick search program coupled with density functional theory calculations, we investigated the potential energy surfaces of Li₂Al₂H₆ and Li₃Al₃H₆. Then single‐point‐energy coupled‐cluster calculations were performed for the lowest energy structures found. Indeed, the global minima established for Li₂Al₂H₆ and Li₃Al₃H₆ contain the Al₂H₆^2? and Al₃H₆^3? kernels, which are isostructural with ethane (C₂H₆), disilane (Si₂H₆), digermane (Ge₂H₆) and propane (C₃H₈), trisilane (Si₃H₈), trigermane (Ge₃H₈) molecules, respectively. Structural, energetic, and electronic characteristics of the Li₂Al₂H₆ and Li₃Al₃H₈ compounds are presented and the viability of their synthesis is discussed.     

Sol-gel synthesis of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte

A modified sol-gel process was studied as applied to synthesize a lithium-conducting solid electrolyte of composition Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) using water-soluble salts Al(NO₃)₃ · 9H₂O, LiNO₃ · 3H₂O, and (NH₄)₂HPO₄ and a titanium(IV) citrate complex. As-synthesized samples were characterized using X-ray powder diffraction, DSC/TG, SEM, and impedance spectroscopy. Sintering of as-synthesized amorphous powders at 700°C was found to yield LATP with crystallite sizes of 42–48 nm. Ionic conductivity of the electrolyte measured in the frequency range 25–10⁶ Hz in disks having 86–90% density that were sintered at 1000°C was (3–4) × 10^?4 S/cm. Temperature-dependent ionic conductivity was studied in the range 25–200°C. The activation energy of conduction was determined for LATP.     

Heterocyclic compounds from 3-(4-phenyl) benzoyl propionic acid

3-(4-Phenyl) benzoyl propionic acid was used as the starting material for the synthesisof furanones (2), pyrrolinones (5), pyridazinones (7), benzoxazinones (8) and quinazolinones (9-11). The behaviour of the derivatives of furanones and benzoxazinones toward different nucleophiles is reported.