Fe-Fe bonding in the rhombic Fe4 cores of the Zintl clusters [Fe4E18]4- (E = Sn and Pb).

We report here the synthesis and characterization of two endohedral Zintl-ion clusters, [Fe4Sn18]4- and [Fe4Pb18]4-, which contain rhombic Fe4 cores. The Fe-Fe bond lengths are all below 2.5 Å, distinctly shorter than in the corresponding Cu clusters, indicating the presence of Fe-Fe bonding. Subtle differences in the structure of the Fe4 core between the two clusters suggest that the change in tetrel element causes a change in electronic ground state, with a very short Fe-Fe bond length of 2.328 Å present across the diagonal of the rhombus in the lead case.

Thermodynamics of phase transitions in Zintl clusters from density functional theory: making and breaking of bonds in Ba3Ge4.

Density functional theory, in conjunction with the quasi-harmonic approximation, has been used to study the equilibrium between the orthorhombic and tetragonal phases of Ba3Ge4. A transition from the high-temperature tetragonal phase containing isolated Ge46- units to the low-temperature orthorhombic phase, where precisely half of the Ge46- units are polymerised along one axis, is predicted at 930 K, somewhat higher than the experimental value of 630 K. An analysis of the phonon density of states shows that the lower entropy of the orthorhombic phase is not associated directly with the polymerisation of the Ge46- units, but rather with the contraction of the unit cell, which raises the frequencies of ion-ion modes involving the relative motions of the Ba2+ and Ge46- units. Calculations also predict that a third, as yet unobserved, p-tetragonal phase, where all of the Ge46- units are polymerised to form two separate chains running in orthogonal directions, might be accessible at pressures close to 1 GPa.

Snap-shots of cluster growth: structure and properties of a Zintl ion with an Fe3 core, [Fe3Sn18]4.

The endohedral Zintl-ion cluster [Fe3Sn18]4- contains a linear Fe3 core with short Fe-Fe bond lengths of 2.4300(9) Å. The ground state is a septet, with significant σ and π contributions to the Fe-Fe bonds. The Sn18 cage is made up of two partially fused Sn9 fragments, and is structurally intermediate between [Ni2CdSn18]6-, where the fragments are clearly separated and [Pd2Sn18]4-, where they are completely fused. It therefore represents an intermediate stage in cluster growth. Analysis of the electronic structure suggests that the presence of the linear Fe-Fe-Fe unit is an important factor in directing reactions towards fusion of the two Sn9 units rather than the alternative of oligomerization via exo bond formation.

Synthesis and Characterization of [Fe3 (As3 )3 (As4 )]3- , a Binary Fe/As Zintl Cluster With an Fe3 Core.

We report here the synthesis and structural characterization of the first binary iron arsenide cluster anion, [Fe3 (As3 )3 (As4 )]3- , present in both [K([2.2.2]crypt)]3 [Fe3 (As3 )3 (As4 )] (1) and [K(18-crown-6)]3 [Fe3 (As3 )3 (As4 )]⋅en (2). The cluster contains an Fe3 triangle with three short Fe-Fe bond lengths (2.494(1) Å, 2.459(1) Šand 2.668(2) Šfor 1, 2.471(1) Å, 2.473(1) Šand 2.660(1) Šfor 2), bridged by a 2-butene-like As4 unit. An analysis of the electronic structure using DFT reveals a triplet ground state with direct Fe-Fe bonds stabilizing the Fe3 core.

High- versus Low-Spin Ni2+ in Elongated Octahedral Environments: Sr2NiO2Cu2Se2, Sr2NiO2Cu2S2, and Sr2NiO2Cu2(Se1-x S x )2.

Sr2NiO2Cu2Se2, comprising alternating [Sr2NiO2]2+ and [Cu2Se2]2- layers, is reported. Powder neutron diffraction shows that the Ni2+ ions, which are in a highly elongated NiO4Se2 environment with D4h symmetry, adopt a high-spin configuration and carry localized magnetic moments which order antiferromagnetically below ∼160 K in a √2a × âˆš2a × 2c expansion of the nuclear cell with an ordered moment of 1.31(2) µB per Ni2+ ion. The adoption of the high-spin configuration for this d 8 cation in a pseudo-square-planar ligand field is supported by consideration of the experimental bond lengths and the results of density functional theory (DFT) calculations. This is in contrast to the sulfide analogue Sr2NiO2Cu2S2, which, according to both experiment and DFT calculations, has a much more elongated ligand field, more consistent with the low-spin configuration commonly found for square-planar Ni2+, and accordingly, there is no evidence for magnetic moment on the Ni2+ ions. Examination of the solid solution Sr2NiO2Cu2(Se1-x S x )2 shows direct evidence from the evolution of the crystal structure and the magnetic ordering for the transition from high-spin selenide-rich compounds to low-spin sulfide-rich compounds as a function of composition. Compression of Sr2NiO2Cu2Se2 up to 7.2 GPa does not show any structural signature of a change in the spin state. Consideration of the experimental and computed Ni2+ coordination environments and their subtle changes as a function of temperature, in addition to transitions evident in the transport properties and magnetic susceptibilities in the end members, Sr2NiO2Cu2Se2 and Sr2NiO2Cu2S2, suggest that simple high-spin and low-spin models for Ni2+ may not be entirely appropriate and point to further complexities in these compounds.

A Zintl Cluster for Transition Metal-Free Catalysis: C═O Bond Reductions.

The first fully characterized boron-functionalized heptaphosphide Zintl cluster, [(BBN)P7]2- ([1]2-), is synthesized by dehydrocoupling [HP7]2-. Dehydrocoupling is a previously unprecedented reaction pathway to functionalize Zintl clusters. [Na(18-c-6)]2[1] was employed as a transition metal-free catalyst for the hydroboration of aldehydes and ketones. Moreover, the greenhouse gas carbon dioxide (CO2) was efficiently and selectively reduced to methoxyborane. This work represents the first examples of Zintl catalysis where the transformation is transition metal-free and where the cluster is noninnocent.

Synthesis and characterisation of the ternary intermetalloid clusters {M@[As8(ZnMes)4]}3- (M = Nb, Ta) from binary [M@As8]3- precursors.

The development of rational synthetic routes to inorganic arsenide compounds is an important goal because these materials are finding applications in many areas of materials science. In this paper, we show that the binary crown clusters [M@As8]3- (M = Nb, Ta) can be used as synthetic precursors which, when combined with ZnMes2, generate ternary intermetalloid clusters with 12-vertex cages, {M@[As8(ZnMes)4]}3- (M = Nb, Ta). Structural studies are complemented by mass spectrometry and an analysis of the electronic structure using DFT. The synthesis of these clusters presents new opportunities for the construction of As-based nanomaterials.

Missing Link in the Growth of Lead-Based Zintl Clusters: Isolation of the Dimeric Plumbaspherene [Cu4Pb22]4.

We report here the structure of an endohedral plumbaspherene, [Cu4Pb22]4-, the gold analogue of which was previously postulated to be a "missing link" in the growth of larger clusters containing three and four icosahedral subunits. The cluster contains two [Cu2Pb11]2- subunits linked through a Cu2Pb4 trigonal antiprism. Density functional theory reveals that the striking ability of mixed Pb/coinage metal Zintl clusters to oligomerize and, in the case of Au, to act as a site of nucleation for additional metal atoms, is a direct consequence of their nd10(n + 1)s0 configuration, which generates both a low-lying (n + 1)s-based LUMO and also a high-lying Pb-centered HOMO. Cluster growth and nucleation is then driven by this amphoteric character, allowing the clusters to form donor-acceptor interactions between adjacent icosahedral units or to additional metal atoms.

Sequential Pressure-Induced B1-B2 Transitions in the Anion-Ordered Oxyhydride Ba2YHO3.

We present a detailed experimental and computational investigation of the influence of pressure on the mixed-anion oxyhydride phase Ba2YHO3, which has recently been shown to support hydride conductivity. The unique feature of this layered perovskite is that the oxide and hydride anions are segregated into distinct regions of the unit cell, in contrast to the disordered arrangement in closely related Ba2ScHO3. Density functional theory (DFT) calculations reveal that the application of pressure drives two sequential B1-B2 transitions in the interlayer regions from rock salt to CsCl-type ordering, one in the hydride-rich layer at approximately 10 GPa and another in the oxide-rich layer at 35-40 GPa. To verify the theoretical predictions, we experimentally observe the structural transition at 10 GPa using high-pressure X-ray diffraction (XRD), but the details of the structure cannot be solved due to peak broadening of the XRD patterns. We use DFT to explore the structural impact of pressure on the atomic scale and show how the pressure-dependent properties can be understood in terms of simple electrostatic engineering.

Evolution of Vibrational Spectra in the Manganese-Silicon Clusters Mn2Sin, n = 10, 12, and 13, and Cationic [Mn2Si13].

A comparison of DFT-computed and measured infrared spectra reveals the ground state structures of a series of gas-phase silicon clusters containing a common Mn2 unit. Mn2Si12 and [Mn2Si13]+ are both axially symmetric, allowing for a clean separation of the vibrational modes into parallel (a1) and perpendicular (e1) components. Information about the Mn-Mn and Mn-Si bonding can be extracted by tracing the evolution of these modes as the cluster increases in size. In [Mn2Si13]+, where the antiprismatic core is capped on both hexagonal faces, a relatively simple spectrum emerges that reflects a pseudo-D6d geometry. In cases where the cluster is more polar, either because there is no capping atom in the lower face (Mn2Si12) or the capping atom is present but displaced off the principal axis (Mn2Si13), the spectra include additional features derived from vibrational modes that are forbidden in the parent antiprism.

Synthesis and Characterization of Ternary Clusters Containing the [As16]10- Anion, [MM'As16]4- (M = Nb or Ta; M' = Cu or Ag).

The [Nb@As8]3- anion was first isolated from solution in 1986, and a number of isostructural [M@Pn8]n- clusters (M = Nb, Cr, or Mo; Pn = As or Sb; n = 2 or 3) have since been reported. We show here how anions of this class can be used as synthetic precursors that, in combination with sources of low-valent late transition metals (Cu and Ag), generate ternary polyarsenide cluster anions with unprecedented structural motifs. Chain type [MM'As16]4- (M = Nb or Ta; M' = Cu or Ag) units are found in compounds 2-5. These clusters contain a nortricyclane-like As7 cage and a [M@As8] crown, linked by a single As atom, and represent a fusion of two quite distinct branches of polyarsenide chemistry. Our analysis of the electronic structure confirms that the cluster retains many of the features of the component units. Electrospray ionization mass spectrometry reveals a series of smaller component ions containing 8-12 As atoms, the density functional theory-computed structures of which can be understood in terms of the pseudoelement concept. This work not only presents a new type of coordination mode for As clusters but also offers a point of entry for the rational design of multinary arsenic-based materials.

Electronic structure and bonding in endohedral Zintl clusters.

Endohedral Zintl clusters-multi-metallic anionic molecules in which a d-block or f-block metal atom is enclosed by p-block (semi)metal atoms-are very topical in contemporary inorganic chemistry. Not only do they provide insight into the embryonic states of intermetallic compounds and show promise in catalytic applications, they also shed light on the nature of chemical bonding between metal atoms. Over the past two decades, a plethora of endohedral Zintl clusters have been synthesized, revealing a fascinating diversity of molecular architectures. Many different perspectives on the bonding in them have emerged in the literature, sometimes complementary and sometimes conflicting, and there has been no concerted effort to classify the entire family based on a small number of unifying principles. A closer look, however, reveals distinct patterns in structure and bonding that reflect the extent to which valence electrons are shared between the endohedral atom and the cluster shell. We show that there is a much more uniform relationship between the total valence electron count and the structure and bonding patterns of these clusters than previously anticipated. All of the p-block (semi)metal shells can be placed on a ladder of total valence electron count that ranges between 4n+2 (closo deltahedra), 5n (closed, three-bonded polyhedra) and 6n (crown-like structures). Although some structural isomerism can occur for a given electron count, the presence of a central metal cation imposes a preference for rather regular and approximately spherical structures which maximise electrostatic interactions between the metal and the shell. In cases where the endohedral metal has relatively accessible valence electrons (from the d or f shells), it can also contribute its valence electrons to the total electron count of the cluster shell, raising the effective electron count and often altering the structural preferences. The electronic situation in any given cluster is considered from different perspectives, some more physical and some more chemical, in a way that highlights the important point that, in the end, they explain the same situation. This article provides a unifying perspective of bonding that captures the structural diversity across this diverse family of multimetallic clusters.

A linear metal-metal bonded tri-iron single-molecule magnet.

The linear trinuclear complex cation [Fe3(DpyF)4]2+ was prepared as [Fe3(DpyF)4](BF4)2·2CH3CN. With large Fe-Fe distances of 2.78 Å, this complex demonstrates intramolecular ferromagnetic coupling between the anisotropic FeII centers (J/kB = +20.9(5) K) giving an ST = 6 ground state and exhibits single-molecule magnet properties.

Open Shells in Endohedral Clusters: Structure and Bonding in the [Fe2@Ge16]4- Anion and Comparison to Isostructural [Co2@Ge16]4.

The anionic cluster [Fe2@Ge16]4- has been characterized and shown to be isostructural to the known D2h-symmetric α isomer of the cobalt analogue [Co2@Ge16]4-. Together with the known pair of compounds [Co@Ge10]3- and [Fe@Ge10]3-, the title compound completes a set of four closely related germanium clusters that allow us to explore how the metal-metal and metal-cage interactions evolve as a function of size and of the identity of the metal. The results of spin-unrestricted density functional theory (DFT) and multiconfigurational self-consistent field (MC-SCF) calculations present a consistent picture of the electronic structure where transfer of electron density from the metal to the cage is significant, particularly in the Fe clusters where the exchange stabilization of unpaired spin density is an important driving force.

Solution-Based Group 14 Zintl Anions: New Frontiers and Discoveries.

ConspectusGroup 14 Zintl anions [Ex]q- (E = Si-Pb, x = 4, 5, 9, 10) are synthetically accessible, and their diverse chemical reactivity makes them valuable synthons in the construction of larger nanoclusters with remarkable structures, intriguing patterns of chemical bonding, and tunable physical and chemical properties. A plethora of novel cluster anions have now been isolated from the reactions of polyanionic [Ex]q- precursors with low-valent d-/f-block metal complexes, main-group organometallics, or organics in polar aprotic solvents. The range of products includes intermetalloid clusters with transition metal atom(s) embedded in main-group element cages, organometallic Zintl anions in which [Ex]q- acts as a ligand, intermetallic Zintl anions where [Ex]q- is bridged by ligand-free transition metal atom(s), organo-Zintl anions where [Ex]q- is functionalized with organic-group(s), and oligomers formed through oxidative coupling reactions. The synthesis and characterization of these unconventional complexes, where important contributions to stability come from ionic, covalent, and metal-metal bonds as well as weaker aurophilic and van der Waals interactions, extend the boundaries of coordination chemistry and solid-state chemistry. Substantial progress has been made in this field over the past two decades, but there are still many mysteries to unravel related to the cluster growth mechanism and the controllable synthesis of targeted clusters, along with the remarkable and diverse patterns of chemical bonding that present a substantial challenge to theory. In this Account, we hope to shed some light on the relationship between structure, electronic properties, and cluster growth by highlighting selected examples from our recent work on homoatomic deltahedral [Ex]q- anions, including (1) germanium-based Zintl clusters, such as the supertetrahedral intermetallic clusters [M6Ge16]4- (M = Zn, Cd) and the sandwich cluster {(Ge9)2[η6-Ge(PdPPh3)3]}4- with a heterometallic Ge@Pd3 interlayer; (2) tin-based intermetalloid clusters [Mx@Sny]q- and the application of [Co@Sn9]4- in bottom-up synthesis; and (3) lead clusters with precious metal cores, including the largest Zintl anion [Au12Pb44]8-. In addition to their intrinsic appeal from a structural and electronic perspective, these new cluster anions also show promise as precursors for the development of new materials with applications in heterogeneous catalysis, where we have recently reported the selective reduction of CO2.

A family of lead clusters with precious metal cores.

Gold nanoparticles have been used for centuries, both for decoration and in medical applications. More recently, many of the major advances in cluster chemistry have involved well-defined clusters containing tens or hundreds of atoms, either with or without a ligand shell. In this paper we report the synthesis of two gold/lead clusters, [Au8Pb33]6- and [Au12Pb44]8-, both of which contain nido [Au@Pb11]3- icosahedra surrounding a core of Au atoms. Analogues of these large clusters are not found in the corresponding Ag chemistry: instead, the Ag-centered nido icosahedron, [Ag@Pb11]3-, is the only isolated product. The structural chemistry, along with the mass spectrometry which shows the existence of [Au2Pb11]2- but not [Ag2Pb11]2-, leads us to propose that the former species is the key intermediate in the growth of the larger clusters. Density functional theory indicates that secondary π-type interactions between the [Au@Pb11]3- ligands and the gold core play a significant part in stabilizing the larger clusters.

[Cu4@E18]4- (E = Sn, Pb): Fused Derivatives of Endohedral Stannaspherene and Plumbaspherene.

We report the synthesis of two new cluster anions, [Cu4@E18]4- (E = Sn, Pb), in which a Cu4 subunit is incorporated into a continuous E18 tetrel cage. Both anions are characterized by X-ray crystallography and mass spectrometry, complemented by quantum-chemical calculations that highlight the relationships to known Zintl clusters, including the stannaspherenes and plumbaspherenes [M@Sn12]q- and [M@Pb12]q-, the Matryoshka bronze [Sn@Cu12@Sn20]12-, and also [Pd2@E'18]4- (E' = Ge, Sn).

Linkage Isomerism Leading to Contrasting Carboboration Chemistry: Access to Three Constitutional Isomers of a Borylated Phosphaalkene.

We describe the reactivity of two linkage isomers of a boryl-phosphaethynolate, [B]OCP and [B]PCO (where [B]=N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), towards tris- (pentafluorophenyl)borane (BCF). These reactions afforded three constitutional isomers all of which contain a phosphaalkene core. [B]OCP reacts with BCF through a 1,2 carboboration reaction to afford a novel phosphaalkene, E-[B]O{(C6 F5 )2 B}C=P(C6 F5 ), which subsequently undergoes a rearrangement process involving migration of both the boryloxy and pentafluorophenyl substituents to afford Z-{(C6 F5 )2 B}(C6 F5 )C=PO[B]. By contrast, [B]PCO undergoes a 1,3-carboboration process accompanied by migration of the N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl to the carbon centre.

Structural, spectroscopic and electronic properties of a family of face-shared bi-octahedral Ru25+/6+ complexes with a bridging 2,5-di(2-pyridyl)pyrrolide ligand.

A family of Ru2 dimers, [Ru2(µ-κ2N,N':κ2N',N''-dpp)2(µ-X)(X)2]q+ (X = Cl, Br, q = 0 and X = I, q = 1) is synthesized from a [Ru2(OAc)4Cl] paddlewheel starting material. The neutral products are mixed-valence Ru25+ dimers with a Ru-Ru bond order of 0.5, while the cationic iodide is a Ru26+ dimer with formal bond order of 1.0. The Ru-Ru distance is strikingly independent of the identity of the halide and the oxidation state of ruthenium, most likely a consequence of the small bridging nitrogen which constrains the geometry. The spectroscopic properties (EPR, UV/Vis) of the Br complex are consistent with a large σ-σ* splitting in [Ru2(µ-κ2N,N':κ2N',N''-dpp)2(µ-Br)(Br)2].

Structural isomerism in the [(Ni@Sn9)In(Ni@Sn9)]5- Zintl ion.

A new Zintl cluster, [(Ni@Sn9)In(Ni@Sn9)]5-, has been isolated in two distinct isomeric forms, one where both Ni@Sn9 units are coordinated to the bridging In atom in an η3- mode, the other where one is η3- and the other η4-. Density functional theory indicates that the energetic separation between these two structures is minimal, suggesting that crystal packing plays a decisive role in the structural chemistry. A comparison of the electronic structure of [(Ni@Sn9)In(Ni@Sn9)]5- with [(Ni@Ge9)Ni(Ni@Ge9)]4-, which has four fewer valence electrons, sheds some light on possible mechanisms that lead to the fusion of cluster fragments.