F-block Metal Complexes Research Articles

Effect of La3+ on the Formation of Endohedral Zintl Clusters Featuring In/Bi Shells.

Investigating the interactions of f-block metal ions with p-block polyanions in multinary cluster compounds is becoming increasingly attractive but remains a challenge in terms of both the synthetic approach and the control of the structures that are formed during the syntheses. So far, two types of reactions were dominant for the formation of corresponding clusters: the reaction of binary anions of p-block elements in 1,2-diamino-ethane (en) solutions or the reaction of organobismuth compounds with corresponding f-block metal complexes in THF. Herein, we report the synthesis of [La@In2Bi11]4- (1) and its doubly μ-Bi-bridged analogue in the doubly [K(crypt-222)]+-coordinated {[K(crypt-222)]2[La@In2Bi11](μ-Bi)2[La@In2Bi11]}4- (2) as their [K(crypt-222)]+ salts [K(crypt-222)]41 and [K(crypt-222)]42, respectively, achieved by reactions of [InMes3] and [La(C5Me4H)3] (Mes = mesityl, C5Me4H = tetramethylcyclopentadienyl) with K10Ga3Bi6.65/crypt-222 (crypt-222 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) in en. In the absence of [La(C5Me4H)3], the otherwise unchanged reactions afford the anions [Bi6(InMes)(InMes2)]3- (3) and [Mes3In-InMes3]2- (4) instead, which can be isolated as their [K(crypt-222)]+ salts [K(crypt-222)]33 and [K(crypt-222)]24·tol (tol = toluene), respectively. The {Bi6} fragment observed in anion 3 is assumed to be one of the key intermediates not only toward the formation of 1 and 2 but also on the way to more general bismuth rich compounds.

Expanding the Coordination of f-Block Metals with Tris[2-(2-methoxyethoxy)ethyl]amine: From Molecular Complexes to Cage-like Structures.

Low-valent f-block metals have intrinsic luminescence, electrochemical, and magnetic properties that are modulated with ligands, causing the coordination chemistry of these metals to be imperative to generating critical insights needed to impact modern applications. To this end, we synthesized and characterized a series of twenty-seven complexes of f-metal ions including EuII, YbII, SmII, and UIII and hexanuclear clusters of LaIII and CeIII to study the impact of tris[2-(2-methoxyethoxy)ethyl]amine, a flexible acyclic analogue of the extensively studied 2.2.2-cryptand, on the coordination chemistry and photophysical properties of low-valent f-block metals. We demonstrate that the flexibility of the ligand enables luminescence tunability over a greater range than analogous cryptates of EuII in solution. Furthermore, the ligand also displays a variety of binding modes to f-block metals in the solid state that are inaccessible to cryptates of low-valent f-block metals. In addition to serving as a ligand for f-block metals of various sizes and oxidation states, tris[2-(2-methoxyethoxy)ethyl]amine also deprotonates water molecules coordinated to trivalent triflate salts of f-block metal ions, enabling the isolation of hexanuclear clusters containing either LaIII or CeIII. The ligand was also found to bind more tightly to YbII and UIII in the solid state compared to 2.2.2-cryptand, suggesting that it can play a role in the isolation of other low-valent f-block metals such CfII, NpIII, and PuIII. We expect that our findings will inspire applications of tris[2-(2-methoxyethoxy)ethyl]amine in the design of light-emitting diodes and the synthesis of extremely reducing divalent f-block metal complexes that are of interest for a wide range of applications.

S-Block Metal Catalysts for the Hydroboration of Unsaturated Bonds.

The addition of a B–H bond to an unsaturated bond (polarized or unpolarized) is a powerful and atom-economic tool for the synthesis of organoboranes. In recent years, s-block organometallics have appeared as alternative catalysts to transition-metal complexes, which traditionally catalyze the hydroboration of unsaturated bonds. Because of the recent and rapid development in the field of hydroboration of unsaturated bonds catalyzed by alkali (Li, Na, K) and alkaline earth (Mg, Ca, Sr, Ba) metals, we provide a detailed and updated comprehensive review that covers the synthesis, reactivity, and application of s-block metal catalysts in the hydroboration of polarized as well as unsaturated carbon–carbon bonds. Moreover, we describe the main reaction mechanisms, providing valuable insight into the reactivity of the s-block metal catalysts. Finally, we compare these s-block metal complexes with other redox-neutral catalytic systems based on p-block metals including aluminum complexes and f-block metal complexes of lanthanides and early actinides. In this review, we aim to provide a comprehensive, authoritative, and critical assessment of the state of the art within this highly interesting research area.

Efficient multicomponent processes for synthesis of novel poly-nuclear hetero aryl substituted terpyridine scaffolds: Single crystal XRD study

We studied the synthesis of novel terpyridine scaffolds from poly-nuclear and hetero-aryl aldehydes by the multicomponent condensation reactions with various acetyl pyridine derivatives in the presence of ammonium hydroxide. We have synthesised highly substituted pyridine scaffolds by different poly-nuclear and heterocyclic molecules that are not easily accessed by conventional methods. Comparative studies of two different processes catalysed by potassium hydroxide and pyrrolidine have been performed and presented in this report. The structures of all the newly prepared terpyridine molecules have been well established by preforming various spectral analysis and single crystal XRD studies for selected molecules. This approach addressed some structural miscellany concerns currently facing in photo-luminescent chemistry, and the derived hybrid pyridines could be used as suitable precursors for the synthesis of related photo-luminescent systems. The prepared scaffolds as such and their d-block or f-block metal complexes and coordination polymers may provide an efficient candidate for photo-luminescent chemistry.

Regioselective Hydrosilylation of Olefins Catalyzed by a Molecular Calcium Hydride Cation.

Chemo‐ and regioselectivity are often difficult to control during olefin hydrosilylation catalyzed by d‐ and f‐block metal complexes. The cationic hydride of calcium [CaH]+ stabilized by an NNNN macrocycle was found to catalyze the regioselective hydrosilylation of aliphatic olefins to give anti‐Markovnikov products, while aryl‐substituted olefins were hydrosilyated with Markovnikov regioselectivity. Ethylene was efficiently hydrosilylated by primary and secondary hydrosilanes to give di‐ and monoethylated silanes. Aliphatic hydrosilanes were preferred over other commonly employed hydrosilanes: Arylsilanes such as PhSiH3 underwent scrambling reactions promoted by the nucleophilic hydride, while alkoxy‐ and siloxy‐substituted hydrosilanes gave isolable alkoxy and siloxy calcium derivatives.

Highly Electron-Rich β-Diketiminato Systems: Synthesis and Coordination Chemistry of Amino-Functionalized "N-nacnac" Ligands.

The synthesis of a class of electron-rich amino-functionalized β-diketiminato (N-nacnac) ligands is reported, with two synthetic methodologies having been developed for systems bearing backbone NMe2 or NEt2 groups and a range of N-bound aryl substituents. In contrast to their (Nacnac)H counterparts, the structures of the protio-ligands feature the bis(imine) tautomer and a backbone CH2 group. Direct metalation with lithium, magnesium, or aluminium alkyls allows access to the respective metal complexes through deprotonation of the methylene function; in each case X-ray structures are consistent with a delocalized imino-amide ligand description. Transmetalation using lithium N-nacnac complexes is then exploited to access p- and f-block metal complexes, which allow for like-for-like benchmarking of the N-nacnac ligand family against their more familiar Nacnac counterparts. In the case of SnII , the degree of electronic perturbation effected by introduction of the backbone NR2 groups appears to be constrained by the inability of the amino group to achieve effective conjugation with the N2 C3 heterocycle. More obvious divergence from established structural norms is observed for complexes of the harder YbII ion, with azaallyl/imino and even azaallyl/NMe2 coordination modes being demonstrated by X-ray crystallography.

Magnesium(I) Dimers Bearing Tripodal Diimine-Enolate Ligands: Proficient Reagents for the Controlled Reductive Activation of CO2 and SO2.

The first examples of magnesium(I) dimers bearing tripodal ligands, [(Mg{κ(3) -N,N',O-(ArNCMe)2 (OCCPh2 )CH})2 ] [Ar=2,6-iPr2 C6 H3 (Dip) 7, 2,6-Et2 C6 H3 (Dep) 8, or mesityl (Mes) 9] have been prepared by post-synthetic modification of the β-diketiminato ligands of previously reported magnesium(I) systems, using diphenylketene, OCCPh2 . In contrast, related reactions between β-diketiminato magnesium(I) dimers and the isoelectronic ketenimine, MesNCCPh2 , resulted in reductive insertion of the substrate into the MgMg bond of the magnesium(I) reactant, and formation of [{(Nacnac)Mg}2 {μ-κ(2) -N,C-(Mes)NCCPh2 }] (Nacnac=[(ArNCMe)2 CH](-) ; Ar=Dep 10 or Mes 11). Reactions of the four-coordinate magnesium(I) dimer 8 with excess CO2 are readily controlled, and cleanly give carbonate [(LMg)2 (μ-κ(2) :κ(2) -CO3 )] 12 (L=[κ(3) -N,N',O-(DepNCMe)2 (OCCPh2 )CH](-) ; thermodynamic product), or oxalate [(LMg)2 (μ-κ(2) :κ(2) -C2 O4 )] 13 (kinetic product), depending on the reaction temperature. Compound 12 and CO are formed by reductive disproportionation of CO2 , whereas 13 results from reductive coupling of two molecules of the gas. Treatment of 8 with an excess of N2 O cleanly gives the μ-oxo complex [(LMg)2 (μ-O)] 14, which reacts facilely with CO2 to give 12. This result presents the possibility that 14 is an intermediate in the formation of 12 from the reaction of 8 and CO2 . In contrast to its reactions with CO2 , 8 reacts with SO2 over a wide temperature range to give only one product; the first example of a magnesium dithionite complex, [(LMg)2 (μ-κ(2) :κ(2) -S2 O4 )] 16, which is formed by reductive coupling of two molecules of SO2 , and is closely related to f-block metal dithionite complexes derived from similar SO2 reductive coupling processes. On the whole, this study strengthens previously proposed analogies between the reactivities of magnesium(I) systems and low-valent f-block metal complexes, especially with respect to small molecule activations.

The reductive disproportionation of CO2 using a magnesium(i) complex: analogies with low valent f-block chemistry

The dimeric magnesium(I) complex, [{(DipNacnac)Mg}2] (DipNacnac = [(DipNCMe)2CH]−, Dip = C6H3Pri2-2,6), reacts with 2 equivalents of CO2 to give a high yield of the MgII carbonate complex, [{(DipNacnac)Mg}2(μ-κ2:κ2-CO3)], and CO via a reductive disproportionation process. The MgII oxalate, [{(DipNacnac)Mg}2(μ-C2O4)], is a very low yield by-product of the reaction. Reducing the carbonate complex with elemental potassium regenerates the MgI starting material. The carbonate complex is shown to form via a stepwise process involving the oxo-bridged intermediate, [{(DipNacnac)Mg}2(μ-O)], which rapidly reacts with stoichiometric CO2 to give [{(DipNacnac)Mg}2(μ-κ2:κ2-CO3)]. The oxo-bridged intermediate has been rationally synthesised via the reaction of [{(DipNacnac)Mg}2] with N2O, and treated with THF to give the adduct, [{(THF)(DipNacnac)Mg}2(μ-O)]. The complex, [{(DipNacnac)Mg}2(μ-O)], reacts with the CO2 isoelectronic analogues, CS2 and CyNCNCy (Cy = cyclohexyl) to give the complexes, [{(DipNacnac)Mg}2(μ-κ2:κ2-CS2O)] and [{(DipNacnac)Mg}2{μ-κ2:κ2-C(NCy)2O}]. Rearrangement of the dithiocarbonate coordination mode of the former occurs upon treatment with diethyl ether, giving the unsymmetrical complex, [{(DipNacnac)Mg}(μ-κ2(S,S′):κ1(O)-CS2O){Mg(DipNacnac)(OEt2)}]. The majority of the complexes prepared in this study were crystallographically characterised. Taken as a whole, this study demonstrates that magnesium(I) dimers can display very similar reactivity, with respect to small molecules activations, as do SmII and UIII compounds. Accordingly, magnesium(I) compounds hold considerable potential as cheaper, less toxic, non-radioactive and diamagnetic alternatives to low valent f-block metal complexes in this realm.

ChemInform Abstract: Paramagnetic Metal Complexes of Diamido Donor Ligands

AbstractReview: 72 refs.

Synthesis, mesomorphic and photo-physical properties of few d- and f- block metals coordinated to polar Schiff's bases

The synthesis, liquid crystalline and optical properties of polar Schiff's bases, viz. N-(4-n-hexadecyloxysali cylidene)-4′-substituted anilines with methyl, nitro and cyano substituents in the 4-position of N-aryl moiety and their d- and f-block metal complexes, are presented. The polar ligands exhibited a smectic A phase, while methyl homologue exhibited a nematic phase. The majority of the complexes exhibited a smectic A phase with some of them exhibiting smectic E phases. The ultraviolet-visible and photo-physical properties of the ligands and complexes are also discussed.

Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl62– (M = Ti, Zr, Hf, U) and UOCl5– Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory

Chlorine K-edge X-ray absorption spectroscopy (XAS) and ground-state and time-dependent hybrid density functional theory (DFT) were used to probe the electronic structures of O(h)-MCl(6)(2-) (M = Ti, Zr, Hf, U) and C(4v)-UOCl(5)(-), and to determine the relative contributions of valence 3d, 4d, 5d, 6d, and 5f orbitals in M-Cl bonding. Spectral interpretations were guided by time-dependent DFT calculated transition energies and oscillator strengths, which agree well with the experimental XAS spectra. The data provide new spectroscopic evidence for the involvement of both 5f and 6d orbitals in actinide-ligand bonding in UCl(6)(2-). For the MCl(6)(2-), where transitions into d orbitals of t(2g) symmetry are spectroscopically resolved for all four complexes, the experimentally determined Cl 3p character per M-Cl bond increases from 8.3(4)% (TiCl(6)(2-)) to 10.3(5)% (ZrCl(6)(2-)), 12(1)% (HfCl(6)(2-)), and 18(1)% (UCl(6)(2-)). Chlorine K-edge XAS spectra of UOCl(5)(-) provide additional insights into the transition assignments by lowering the symmetry to C(4v), where five pre-edge transitions into both 5f and 6d orbitals are observed. For UCl(6)(2-), the XAS data suggest that orbital mixing associated with the U 5f orbitals is considerably lower than that of the U 6d orbitals. For both UCl(6)(2-) and UOCl(5)(-), the ground-state DFT calculations predict a larger 5f contribution to bonding than is determined experimentally. These findings are discussed in the context of conventional theories of covalent bonding for d- and f-block metal complexes.

Paramagnetic metal complexes of diamido donor ligands

Recently, considerable attention has been given to the use of multi-dentate amido ligands in the coordination chemistry of a range of transition metals as a means of accessing novel structural motifs and unusual reactivity. Presented herein is a perspective on transition and f-block metal complexes containing diamido donor ligands of the general form [NDN](2-) (D = NR, O, PR). Particular focus is given to paramagnetic metals, which have in general been studied much less than their diamagnetic counterparts despite their potential to exhibit unique structures and diverse reactivity patterns, in addition to their magnetic properties.