Synthesis, polymorphism, and shape complementarity-induced co-crystallization of hexanuclear Co(II) clusters capped by a flexible heteroligand shell.

Polymorphism and co-crystallization have gradually gained attention as new tools in the development of modern crystalline functional materials. However, the study on the selective self-assembly of metal clusters into multicomponent crystals is still in its infancy. Herein, we present the synthesis and characterization of two new heteroleptic hydroxido-acetato and acetato Co(II) clusters [Co6(OH)2(OAc)4(pyret)6] (1) and [Co6(OAc)6(pyret)6] (2) incorporating auxiliary 2-pyrrolidinoethoxylate (pyret) ligands. On this occasion, we revealed that the commonly used thermal procedure for dehydration of cobalt(II) acetate leads to a reagent comprising substantial contamination by cobalt hydroxido moieties. Comprehensive structural analysis of new compounds demonstrated intriguing crystal structure diversity of hydroxido-acetato cluster 1, which represents a rare example of both conformational and packing polymorphism in one compound, originating from the flexibility of organic O,N-ligands in the secondary coordination sphere. Furthermore, both clusters exhibit an interesting propensity for the selective formation of co-crystals 1·2 driven mainly by van der Waals forces and specific shape complementarity between co-formers.

On the Fate of Lithium Ions in Sol-Gel Derived Zinc Oxide Nanocrystals.

Among diverse chemical synthetic approaches to zinc oxide nanocrystals (ZnO NCs), ubiquitous inorganic sol-gel methodology proved crucial for advancements in ZnO-based nanoscience. Strikingly, unlike the exquisite level of control over morphology and size dispersity achieved in ZnO NC syntheses, the purity of the crystalline phase, as well as the understanding of the surface structure and the character of the inorganic-organic interface, have been limited to vague descriptors until very recently. Herein, ZnO NCs applying the standard sol-gel synthetic protocol are synthesized with zinc acetate and lithium hydroxide and tracked the integration of lithium (Li) cations into the interior and exterior of nanoparticles by combining various techniques, including advanced solid-state NMR methods. In contrast to common views, it is demonstrated that Li+ ions remain kinetically trapped in the inorganic core, enter into a shallow subsurface layer, and generate "swelling" of the surface and interface regions. Thus, this work enabled both the determination of the NCs' structural imperfections and an in-depth understanding of the unappreciated role of the Li+ ions in impacting the doping and the passivation of sol-gel-derived ZnO nanomaterials.

Multinuclear Zinc-Magnesium Hydroxide Carboxylates: A Predesigned Model System for Copolymerization of CO2 with Epoxides.

Among numerous catalysts in the ring-opening copolymerization of epoxides with carbon dioxide (CO2), zinc dicarboxylate complexes are the most common type, and in the family of metal-based homogeneous catalysts, zinc and magnesium complexes have attracted widespread attention. We report on the synthesis and structural characterization of a zinc-magnesium benzoate framework templated by the central hydroxide anion with µ3-κ2:κ2:κ2 coordination mode, [ZnMg2(µ3-OH)(O2CPh)5]n (n = 1 or 2). The resulting heterometallic system forms stable Lewis acid-base adducts with tetrahydrofuran (THF) and cyclohexene oxide (CHO), which crystallize as the hexanuclear zinc-magnesium hydroxide carboxylate cluster [ZnMg2(µ3-OH)(O2CPh)5(L)2]2 (L = THF or CHO). Their X-ray crystal structure analysis revealed that the Zn center prefers 4-fold coordination and the Mg centers demonstrated the ability to accommodate higher coordination numbers, and as a result, the heterocyclic molecules are exclusively bonded to 6-fold Mg atoms. The heteronuclear carboxylate aggregates appeared active in the copolymerization reaction at elevated temperatures to produce an alternating poly(cyclohexene carbonate).

Factors controlling the structure of alkylzinc amidinates: on the role of N-substituents.

Despite various applications of alkylzinc complexes supported by N,N-bidentate ligands in chemistry and materials science, the corresponding organozinc amidinates still represent an insufficiently explored area. To gain a more in-depth understanding of factors controlling the structure and stability of alkylzinc amidinates, we selected benzamidinate and N,N'-diphenylformamidinate ligands as model N,N'-unsubstituted and N,N'-diaryl substituted ligands, respectively, to systematically modify the secondary coordination sphere of the Zn center. A series of new alkylzinc amidinates has been synthesized and their molecular structures identified in both the solid state (single-crystal X-ray crystallography) and solution (NMR and FTIR spectroscopy). The results indicate that [RZnL]x-type amidinate moieties are essentially unstable and tend to undergo Schlenk equilibria-mediated ligand scrambling leading to more thermodynamically stable non-stoichiometric [R2Zn3L4]- and [R3Zn4L5]-type complexes. This process is significantly influenced by the secondary coordination sphere noncovalent interactions as well as the steric hindrance provided by both zinc-bounded alkyl groups and the N-substituents.

A modular design approach to polymer-coated ZnO nanocrystals.

Hybrid materials based on inorganic nanocrystals with organic polymers feature peculiar and fascinating properties and various applications. However, there is still a need for simple synthesis procedures that provide precise control over the polymer/nanocrystal microstructure of these materials. Herein, a novel organometallic approach to polymer-coated ZnO nanocrystals was developed. The presented method merges the initial ring-opening polymerization of ϵ-caprolactone mediated by an organozinc alkoxide initiator and an air-promoted transformation of the resulting macromolecular organozinc species. This one-pot procedure results in quantum-sized ZnO crystals with a core diameter of ca 3 nm coated by poly(ϵ-caprolactone) covalently bonded to the surface. Overall, the ability to create well-defined hybrid composites should provide a unique ability to access various nanosystems.

Non-redox reactivity of V(II) and Fe(II) formamidinates towards CO2 resulting in the formation of novel M(II) carbamates.

Chemical fixation of CO2 is a powerful tool for the preparation of novel multinuclear metal complexes and functional materials. Particularly, the insertion of CO2 into a metal-X bond (X = H, C, N, O) often is a key elementary step in the various processes transforming this greenhouse gas into valuable products. Herein, we report on the reactivity between CO2 and V(II) and Fe(II) complexes supported by N,N'-bis(2,6-diisopropylphenyl)formamidinate ligands (DippF). The reactions proceeded with multiple insertions of CO2 into the M-N bonds leading to the isolation of three novel complexes: [(κ2-DippFCO2)(THF)V(µ-DippFCO2)3V(THF)], [(κ2-DippFCO2)Fe(µ-DippFCO2)2(µ-DippF)Fe(THF)] and [(κ2-DippFCO2)Fe(µ-DippFCO2)3Fe(κ1-DippFH)], which were characterised using single-crystal X-ray diffraction, FTIR and 57Fe Mössbauer spectroscopy (for the diiron compounds). We provide the first well-documented studies of the CO2 reactivity towards the V-N bond and broaden the state-of-the-art of the undeveloped area of the reactivity of low-valent V(II) complexes. Moreover, we showed that the effectivity of the examined CO2 insertion processes strongly depends on the used solvent's characteristics (for the Fe(II) system) and the metal centre's coordination sphere geometry (for the V(II) system).

Tetrahedral M4(µ4-O) Motifs Beyond Zn: Efficient One-Pot Synthesis of Oxido-Amidate Clusters via a Transmetalation/Hydrolysis Approach.

While zinc µ4-oxido-centered complexes are widely used as versatile precursors and building units of functional materials, the synthesis of their analogues based on other transition metals is highly underdeveloped. Herein, we present the first efficient systematic approach for the synthesis of homometallic [M4(µ4-O)L6]-type clusters incorporating divalent transition-metal centers, coated by bridging monoanionic organic ligands. As a proof of concept, we prepared a series of charge-neutral metal-oxido benzamidates, [M4(µ4-O) (NHCOPh)6] (M = Fe, Co, Zn), including iron(II) and cobalt(II) clusters not accessible before. The resulting complexes were characterized using elemental analysis, FTIR spectroscopy, magnetic measurements, and single-crystal X-ray diffraction. Detailed structural analysis showed interesting self-assembly of the tetrahedral clusters into 2D honeycomb-like supramolecular layers driven by hydrogen bonds in the proximal secondary coordination sphere. Moreover, we modeled the magnetic properties of new iron (II) and cobalt (II) clusters, which display a general tendency for antiferromagnetic coupling of the µ4-O/µ-benzamidate-bridged metal centers. The developed synthetic procedure is potentially easily extensible to other M(II)-oxido systems, which will likely pave the way to new oxido clusters with interesting optoelectronic and self-assembly properties and, as a result, will allow for the development of new functional materials not achievable before.

Mechanochemical vs Wet Approach for Directing CO2 Capture toward Various Carbonate and Bicarbonate Networks.

The distinct research areas related to CO2 capture and mechanochemistry are both highly attractive in the context of green chemistry. However, merger of these two areas, i.e., mechanochemical CO2 capture, is still in an early stage of development. Here, the application of biguanidine as an active species for CO2 capture is investigated using both solution-based and liquid-assisted mechanochemical approaches, which lead to a variety of biguanidinium carbonate and bicarbonate hydrogen-bonded networks. We demonstrate that in solution, the formation of the carbonate vs bicarbonate networks can be directed by the organic solvent, while, remarkably, in the liquid-assisted mechanochemical synthesis employing the same solvents as additives, the selectivity in network formation is inversed. In general, our findings support the view of mechanochemistry not only as a sustainable alternative but rather as a complementary strategy to solution-based synthesis.

Exploring the reactivity of homoleptic organozincs towards SO2: synthesis and structure of a homologous series of organozinc sulfinates.

Studies on the reactivity of zinc alkyl compounds towards SO2 are relatively less explored than either oxygenation or hydrolysis reactions. We report on the environmentally friendly and efficient syntheses of a homologous series of [(RSO2)ZnR]n complexes from reactions involving homoleptic R2Zn (R = Me, tBu, Ph) compounds and SO2. Diffusion ordered spectroscopy experiments indicate that the resulting compounds predominately occur as solvated dimers, [(RSO2)ZnR(THF)]2, in THF solution irrespective of the character of the group bonded to the zinc centres. In turn, these organozinc sulfinates exhibit structurally diversified molecular and supramolecular arrangements in the solid state, as evidenced by single-crystal X-ray diffraction studies. The methyl compound crystallises as a one-dimensional polymer, [(MeSO2)ZnMe]n, and the use of tBu2Zn and Ph2Zn leads to molecular aggregates, a tetramer [(tBuSO2)ZntBu]4, and a solvated [(PhSO2)ZnPh]2·2THF dimer, respectively. In addition, new theoretical insights have been gained by modelling the direct trapping of homoleptic organozinc compounds with SO2 using DFT calculations.

A New Look at Molecular and Electronic Structure of Homoleptic Diiron(II,II) Complexes with N,N-Bidentate Ligands: Combined Experimental and Theoretical Study.

Paddlewheel-type binuclear complexes featuring metal-metal bonding have been the subject of widespread interest due to fundamental concern in their electronic structures and potential applications. Here, we explore the molecular and electronic structures of diiron(II,II) complexes with N,N'-diarylformamidinate ligands. While a paddlewheel-type diiron(II,II) complex with N,N'-diphenylformamidinate ligands (DPhF) exhibits the centrosymmetric [Fe2 (µ-DPhF)4 ] structure, a minor alteration in the ligand system, i. e., switching from phenyl to p-tolyl N-substituted formamidinate ligand (DTolF), resulted in the isolation of an unprecedented non-centrosymmetric [Fe(µ-DTolF)3 Fe(κ2 -DTolF)] complex. Both complexes were characterized using single-crystal X-ray diffraction, magnetic measurements, 57 Fe Mössbauer spectroscopy, and cyclic voltammetry along with high-level ab-initio calculations. The results provide a new view on a range of factors controlling the ground-state electronic configuration and structural diversity of homoleptic diiron(II,II) complexes. Model calculations determined that the Mayer bond orders for Fe-Fe interactions are significantly lower than 1 and equal to 0.15 and 0.28 for [Fe2 (µ-DPhF)4 ] and [Fe(µ-DTolF)3 Fe(κ2 -DTolF)], respectively.

Cyclodextrin-Templated Co(II) Grids: Symmetry Control over Supramolecular Topology and Magnetic Properties.

While inherent complexation properties and propensity for self-organization of cyclodextrins (CDs) render them potentially promising scaffolds of magnetic materials, this research area is still at an embryonic stage. We report on the synthesis and structure characterization of a new sandwich-type complex, [(α-CD)2Co3Li6(H2O)9] (α-1), which represents a smaller analogue of the previously characterized [(γ-CD)2Co4Li8(H2O)12] (γ-1) cluster. A comprehensive structural analysis of α-1 and a careful reinvestigation of γ-1 reveal how the symmetry of CD ligands determines the molecular composition and supramolecular arrangements of Co/Li sandwich-type complexes. Furthermore, the first comparative studies of the magnetic properties in this type of system point to subtle differences in the magnetic behavior of both compounds. The sandwich-type complexes α-1 and γ-1 exhibit field-induced slow magnetic relaxation, defining a new family of magnetic materials with a pillared grid-like supramolecular structure composed of weakly interacting CoII centers forming an SMM.

From a Well-Defined Organozinc Precursor to Diverse Luminescent Coordination Polymers Based on Zn(II)-Quinolinate Building Units Interconnected by Mixed Ligand Systems.

Introduction of photoactive building blocks into mixed-ligand coordination polymers appears to be a promising way to produce new advanced luminescent materials. However, rational design and self-assembly of the multi-component supramolecular systems is challenging from both a conceptual and synthetic perspective. Here, we report exploratory studies that investigate the potential of [Zn(q)2]2[tBuZn(OH)]2 complex (q = deprotonated 8-hydroxyquinoline) as an organozinc precursor as well as a mixed-ligand synthetic strategy for the preparation of new luminescent coordination polymers (CPs). As a result we present three new 2D mixed-ligand Zn(II)-quinolinate coordination polymers which are based on various zinc quinolinate secondary building units interconnected by two different organic linker types, i.e., deprotonated 4,4'-oxybisbenzoic acid (H2obc) as a flexible dicarboxylate linker and/or selected bipyridines (bipy). Remarkably, using the title organozinc precursors in a combination with H2obc and 4,4'-bipyridine, a novel molecular zinc quinolinate building unit, [Zn4(q)6(bipy)2(obc)2], was obtained which self-assembled into a chain-type hydrogen-bonded network. The application of the organometallic precursor allowed for its direct reaction with the selected ligands at ambient temperature, avoiding the use of both solvothermal conditions and additional base reagents. In turn, the reaction involving Zn(NO3)2, as a classical inorganic precursor, in a combination with H2obc and bipy led to a novel 1D coordination polymer [Zn2(q)2(NO3)2(bipy)]. While the presence of H2obc was essential for the formation of this coordination polymer, this ditopic linker was not incorporated into the isolated product, which indicates its templating behavior. The reported compounds were characterized by single-crystal and powder X-ray diffraction, elemental analysis as well as UV-Vis and photoluminescence spectroscopy.

Effectiveness of the Oxygenation over Classical Protonolysis Reactions: A Case of Alkylzinc Complexes Incorporating an Aminoalcoholate Ligand.

Alkylzinc aminoalcoholates have emerged as powerful catalysts in organic synthesis and polymerization processes. Despite extensive research, difficulties in the rational design of these catalytic systems and in-depth understanding of their modes of action have hitherto been encountered. Most of the major obstacles stem largely from the relatively limited knowledge of the structure-activity relationship of zinc catalysts. In fact, the key active species are often generated in situ via the protonolysis of the alkylzinc precursors, which precludes their isolation and detailed characterization. Herein, the effectiveness of the oxygenation over the classical protonolysis in the synthesis of zinc alkylperoxides stabilized by an aminoalcoholate ligand is demonstrated. The controlled oxygenation of a tert-butylzinc complex incorporating a pridinolum (prinol) ligand leads to well-defined a dinuclear adduct of a (prinol)ZnOOtBu moiety with the parent tBuZn(prinol) complex and a novel dimer [tBuOOZn(prinol)]2 with terminal alkylperoxide groups. The observed reaction outcomes strongly depend on the reaction conditions. Although sparse examples of heteroleptic adducts of the [RZn(L)]x [ROOZn(L)]y -type are known, the herein reported homoleptic [ROOZn(L)]x aggregate is unprecedented. Strikingly, comparative studies involving reactions between tBuZn(prinol) and tert-butylhydroperoxide or ethanol revealed that the respective seemingly simple zinc alkylperoxides, or zinc alkoxides, respectively, are not accessible via the classical alcoholysis. We believe that these game-changing results concerning multifaceted chemistry of organozinc aminoalcoholates should pave the way for more rational development of various Zn-based catalytic systems.

Stepwise Stress-Induced Transformations of Metal-Organic Polyhedral Cluster-Based Assemblies: Where Conformational and Supramolecular Features Meet.

Understanding the factors governing the formation of supramolecular structures and phase transitions between various forms of molecular crystals is pivotal for developing dynamic, stimuli-responsive materials and polymorph-controlled syntheses. Here, we investigate the pressure-induced dynamic of both the intrinsic molecular structure and the supramolecular network of a predesigned polyhedral oxo-centered zinc cluster incorporating monoanionic N,N'-diphenylformamidinate and featuring N-bonded phenyl groups in close proximity to the primary coordination sphere. We demonstrate that the model oxo cluster is prone to undergoing pressure-induced conformational transformations of the secondary coordination sphere and simultaneous stepwise (initially every second polyhedral molecule undergoes the conformational transformations) and reversible transitions from an ambient phase α to high-pressure phases ß and γ, as single-crystal-to-single-crystal events. The observed phase transitions illustrate the key role of an interplay between the low-energy conformation perturbations and cooperative intra- and intermolecular noncovalent interactions.

A Case Study on the Desired Selectivity in Solid-State Mechano- and Slow-Chemistry, Melt, and Solution Methodologies.

Solution-based syntheses are omnipresent in chemistry but are often associated with obvious disadvantages, and the search for new mild and green synthetic methods continues to be a hot topic. Here, comparative studies in four different reaction media were conducted, that is, the solid-state mechano- and slow-chemistry synthesis, melted phase, and solution protocols, and the impact of the employed solvent-free solid-state versus liquid-phase synthetic approaches was highlighted on a pool of products. A moderately exothermic model reaction system was chosen based on bis(pentafluorophenyl)zinc, (C6 F5 )2 Zn, and 2,2,6,6-tetramethylpiperidinyl oxide (TEMPO) as a stable nitroxyl radical, anticipating that these reagents may offer a unique landscape for addressing kinetic and thermodynamic aspects of wet and solvent-free solid-state processes. In a toluene solution two distinct paramagnetic Lewis acid-base adducts (C6 F5 )2 Zn(η1 -TEMPO) (1) and (C6 F5 )2 Zn(η1 -TEMPO)2 (2) equilibrated, but only 2 was affordable by crystallization. In turn, crystallization from the melt was the only method yielding single crystals of 1. Moreover, the solid-state approaches were stoichiometry sensitive and allowed for the selective synthesis of both adducts by simple stoichiometric control over the substrates. Density functional theory (DFT) calculations were carried out to examine selected structural and thermodynamic features of the adducts 1 and 2. Compound 2 is a unique non-redox active metal complex supported by two nitroxide radicals, and the magnetic studies revealed weak-to-moderate intramolecular antiferromagnetic interactions between the two coordinated TEMPO molecules.

Nanoscale Phase Segregation in Supramolecular π-Templating for Hybrid Perovskite Photovoltaics from NMR Crystallography.

The use of layered perovskites is an important strategy to improve the stability of hybrid perovskite materials and their optoelectronic devices. However, tailoring their properties requires accurate structure determination at the atomic scale, which is a challenge for conventional diffraction-based techniques. We demonstrate the use of nuclear magnetic resonance (NMR) crystallography in determining the structure of layered hybrid perovskites for a mixed-spacer model composed of 2-phenylethylammonium (PEA+) and 2-(perfluorophenyl)ethylammonium (FEA+) moieties, revealing nanoscale phase segregation. Moreover, we illustrate the application of this structure in perovskite solar cells with power conversion efficiencies that exceed 21%, accompanied by enhanced operational stability.

Effect of the proximal secondary sphere on the self-assembly of tetrahedral zinc-oxo clusters.

Metal-oxo clusters can serve as directional and rigid building units of coordination and noncovalent supramolecular assemblies. Therefore, an in-depth understanding of their multi-faceted chemistry is vital for the development of self-assembled solid-state structures of desired properties. Here we present a comprehensive comparative structural analysis of isostructural benzoate, benzamidate, and new benzamidinate zinc-oxo clusters incorporating the [O,O]-, [O,NH]- and [NH,NH]-anchoring donor centers, respectively. We demonstrated that the NH groups in the proximal secondary coordination sphere are prone to the formation of intermolecular hydrogen bonds, which affects the packing of clusters in the crystal structure. Coordination sphere engineering can lead to the rational design of new catalytic sites and novel molecular building units of supramolecular assemblies.

Towards deeper understanding of multifaceted chemistry of magnesium alkylperoxides.

Despite considerable progress in the multifaceted chemistry of non-redox-metal alkylperoxides, the knowledge about magnesium alkylperoxides is in its infancy and only started to gain momentum. Harnessing the well-defined dimeric magnesium tert-butylperoxide [(f5BDI)Mg(µ-η2:η1-OOtBu)]2 incorporating a fluorinated ß-diketiminate ligand, herein, we demonstrate its transformation at ambient temperature to a spiro-type, tetranuclear magnesium alkylperoxide [(f5BDI)2Mg4(µ-OOtBu)6]. The latter compound was characterized by single-crystal X-ray diffraction and its molecular structure can formally be considered as a homoleptic magnesium tert-butylperoxide [Mg(µ-OOtBu)2]2 terminated by two monomeric magnesium tert-butylperoxides. The formation of the tetranuclear magnesium alkylperoxide not only contradicts the notion of the high instability of magnesium alkylperoxides, but also highlights that there is much to be clarified with respect to the solution behaviour of these species. Finally, we probed the reactivity of the dimeric alkylperoxide in model oxygen transfer reactions like the commonly invoked metathesis reaction with the parent alkylmagnesium and the catalytic epoxidation of trans-chalcone with tert-butylhydroperoxide as an oxidant. The results showed that the investigated system is among the most active known catalysts for the epoxidation of enones.

Unravelling Structural Mysteries of Simple Organozinc Alkoxides.

Simple RZnOR' alkoxides are among the first known organozinc compounds, and widespread interest in their multifaced chemistry has been driven by their fundamental significance and potential applications including various catalytic reactions. Nevertheless, their chemistry in solution and in the solid state remains both relatively poorly understood and a subject of constant debate. Herein, the synthesis and structural characterization of long-sought structural forms, a roof-like trimer [(tBuZn)3 (µ-OC(H)Ph2 )2 (µ3 -OC(H)Ph2 )] and a ladder-type tetramer [(PhZn)4 (µ-OC(H)Ph2 )2 (µ3 -OC(H)Ph2 )2 ], incorporating diphenylmethanolate as a model alkoxide ligand, are reported. Both novel aggregates are robust in the solid state and resistant towards mechanical force. By using 1 H NMR and diffusion-order spectroscopy, it is demonstrated that new RZnOR' alkoxides are kinetically labile in solution and readily undergo ligand scrambling, such as in the case of Schlenk equilibrium. The elucidated key structural issues, which have remained undiscovered for decades, significantly advance the chemistry of RZnOR' alkoxides and should support the rational design of zinc alkoxide-based applications.

Structural diversity of ethylzinc derivatives of 3,5-substituted pyrazoles.

Equimolar reactions of Et2Zn with 3,5-dimethylpyrazole (H-pzMe2), 3,5-di-iso-propylpyrazole (H-pziPr2), 3,5-di-tert-butylpyrazole (H-pztBu2) and indazole (H-ind) were investigated in toluene or tetrahydrofuran (as a coordinating solvent). A series of diverse ethylzinc pyrazolates and indazolates were identified using advanced NMR spectroscopy and the single crystal X-ray diffraction techniques. The NMR experiments indicate that dimeric moieties of the general formula [EtZn(pz)]2 or [Et2Zn2(pz)2(THF)] are favoured in solution. Nevertheless, these types of complexes are kinetically labile and tend to undergo ligand scrambling reactions according to the Schlenk equilibrium. For example, the alkyl substituents in the pzMe2 and pziPr2 ligands do not appear to be a strong determinant of the dimeric moieties and the composition of the isolated complexes by crystallisation from the parent reaction mixture varies between spiro-type tri- and tetranuclear aggregates, [Et2Zn3(pz)4(THF)x] (x = 0 or 2) and [Et2Zn4(pz)6(THF)2], respectively. The nonstoichiometric formula of these organozinc derivatives is likely related to both the Schlenk-type equilibria and solubility of the respective moieties. In turn, the high steric demands of the 3,5-di-tert-butylpyrazolate ligand promote the dimeric form in solution and the solid state. Interestingly, the ethylzinc indazolate complex also does not undergo a redistribution reaction and yields a dimer.