Cationic ligands - from monodentate to pincer systems.

For a long time, the small group of cationic ligands stood out as obscure systems within the general landscape of coordinative chemistry. However, this situation has started to change rapidly during the last decade, with more and more examples of metal-coordinated cationic species being reported. The growing interest in these systems is not only of purely academic nature, but also driven by accumulating evidence of their high catalytic utility. Overcoming the inherently poor coordinating ability of cationic species often required additional structural stabilization. In numerous cases this was realized by functionalizing them with a pair of chelating side-arms, effectively constructing a pincer-type scaffold. This comprehensive review aims to encompass all cationic ligands possessing such pincer architecture reported to date. Herein every cationic species that has ever been embedded in a pincer framework is described in terms of its electronic structure, followed by an in-depth discussion of its donor/acceptor properties, based on computational studies (DFT) and available experimental data (IR, NMR or CV). We then elaborate on how the positive charge of these ligands affects the spectroscopic and redox properties, as well as the reactivity, of their complexes, compared to those of the structurally related neutral ligands. Among other systems discussed, this review also surveys our own contribution to this field, namely, the introduction of sulfonium-based pincer ligands and their complexes, recently reported by our group.

Sulfonium Cation in the Service of π-Acid Catalysis.

While still rare, cationic ligands offer much promise as tunable electron-withdrawing ligands for π-acid catalysis. Recently, we introduced pincer-type sulfonium cations into the list of available strongly π-acidic ancillary ligands. However, the M-S bond in sulfonium complexes of these ligands was found highly labile, precluding their catalytic applications. Herein we demonstrate that this obstacle can be overcome by increasing the rigidity of the sulfonium pincer scaffold. X-ray analyses confirm that despite bearing a formal positive charge, the sulfur atom of this newly designed sulfonium ligand maintains its coordination to the Pt(II)-center, while DFT calculations indicate that by doing so it strongly enhances the electrophilic character of the metal. Kinetic studies carried out on three model cycloisomerization reactions prove that such a tris-cationic sulfonium-Pt(II) complex is highly reactive, compared to its thioether-based analogue. This proof-of-concept study presents the first example of employing sulfonium-based ligands in homogeneous catalysis.

Effect of Internal Ligand Strain on Coordination Behavior of PSP Pincer Ligands.

Chelating ligands and most specifically pincer ligands, with their characteristic co-planar binding, usually undergo deformations upon coordination, resulting in a significant ligand strain. Such an effect on the properties of the so formed complex has rarely been explored. This study is an attempt to analyze this strain and its contribution to the overall binding energy and coordination behavior of PSP pincer ligands. Hence, we designed a rigid thioxanthone-based PSP pincer ligand (I) and studied the difference in the coordination properties with the more flexible thioxanthene and thioether-based PSP pincer ligands (II and III). Although with one equivalent of Pd(II) precursor, the three ligands exhibited a similar coordination behavior leading to similar κ3-P,S,P pincer complexes, an in-depth computational analysis pointed out the different contributions of the internal strain energy in lowering the binding energy of these complexes. This effect was clearly reflected when we calculated the enthalpy change of these ligand-exchange reactions. As these exchange reactions are enthalpy-driven, these results could also be confirmed experimentally. With two equivalents of Pd(II), the three ligands diverged in their coordination behavior. Specifically, ligands I and III gave each a binuclear complex, with different coordination modes, whereas the pincer complex of ligand II remained unaffected by excess of Pd(II). Our calculations suggest that the driving force for the formation of binuclear Pd(II) complexes is the relief of the internal ligand strain. With Pt(II), only the mononuclear κ3-P,S,P pincer complexes were obtained irrespectively of the amount of the Pt(II) precursor. In these cases, we assume that kinetic inertness of the formed mononuclear pincer Pt(II) complexes prevents binding of an additional Pt(II) nucleus. This study points out the important role of the internal ligand strain in PSP pincer ligand coordination behavior. We believe that our findings can be extended to other pincer ligands systems as well.

Sulfonium cations as versatile strongly π-acidic ligands.

More than a century old, sulfonium cations are still intriguing species in the landscape of organic chemistry. On one hand they have found broad applications in organic synthesis and materials science, but on the other hand, while isoelectronic to the ubiquitous tertiary phosphine ligands, their own coordination chemistry has been neglected for the last three decades. Here we report the synthesis and full characterization of the first Rh(i) and Pt(ii) complexes of sulfonium. Moreover, for the first time, coordination of an aromatic sulfonium has been established. A thorough computational analysis of the exceptionally short S-Rh bonds obtained attests to the strongly π-accepting nature of sulfonium cations and places them among the best π-acceptor ligands available today. Our calculations also show that embedding within a pincer framework enhances their π-acidity even further. Therefore, in addition to the stability and modularity that these frameworks offer, our pincer complexes might open the way for sulfonium cations to become powerful tools in π-acid catalysis.

Single-Ion Li+, Na+, and Mg2+ Solid Electrolytes Supported by a Mesoporous Anionic Cu-Azolate Metal-Organic Framework.

A novel Cu(II)-azolate metal-organic framework (MOF) with tubular pores undergoes a reversible single crystal to single crystal transition between neutral and anionic phases upon reaction with stoichiometric amounts of halide or pseudohalide salts. The stoichiometric transformation between the two phases allows loading of record amounts of charge-balancing Li+, Na+, and Mg2+ ions for MOFs. Whereas the halide/pseudohalide anions are bound to the metal centers and thus stationary, the cations move freely within the one-dimensional pores, giving rise to single-ion solid electrolytes. The respective Li+-, Na+-, and Mg2+-loaded materials exhibit high ionic conductivity values of 4.4 × 10-5, 1.8 × 10-5, and 8.8 × 10-7 S/cm. With addition of LiBF4, the Li+ conductivity improves to 4.8 × 10-4 S/cm. These are the highest values yet observed for MOF solid electrolytes.

Is iron unique in promoting electrical conductivity in MOFs?

Identifying the metal ions that optimize charge transport and charge density in metal-organic frameworks is critical for systematic improvements in the electrical conductivity in these materials. In this work, we measure the electrical conductivity and activation energy for twenty different MOFs pertaining to four distinct structural families: M2(DOBDC)(DMF)2 (M = Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+); H4DOBDC = 2,5-dihydroxybenzene-1,4-dicarboxylic acid; DMF = N,N-dimethylformamide), M2(DSBDC)(DMF)2 (M = Mn2+, Fe2+; H4DSBDC = 2,5-disulfhydrylbenzene-1,4-dicarboxylic acid), M2Cl2(BTDD)(DMF)2 (M = Mn2+, Fe2+, Co2+, Ni2+; H2BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i]dibenzo[1,4]dioxin), and M(1,2,3-triazolate)2 (M = Mg2+, Mn2+, Fe2+, Co2+, Cu2+, Zn2+, Cd2+). This comprehensive study allows us to single-out iron as the metal ion that leads to the best electrical properties. The iron-based MOFs exhibit at least five orders of magnitude higher electrical conductivity and significantly smaller charge activation energies across all different MOF families studied here and stand out materials made from all other metal ions considered here. We attribute the unique electrical properties of iron-based MOFs to the high-energy valence electrons of Fe2+ and the Fe3+/2+ mixed valency. These results reveal that incorporating Fe2+ in the charge transport pathways of MOFs and introducing mixed valency are valuable strategies for improving electrical conductivity in this important class of porous materials.

Reversible Capture and Release of Cl2 and Br2 with a Redox-Active Metal-Organic Framework.

Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable nonvolatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal-organic framework (MOF) to produce stable and safe-to-handle Co(III) materials featuring terminal Co(III)-halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reduction to Co(II), and concomitant release of elemental halogens. The reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, as the parent cobaltous MOF retains its crystallinity and porosity even after three oxidation/reduction cycles. These results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.

Nitrogen Lewis Acids.

Being a major conception of chemistry, Lewis acids have found countless applications throughout chemical enterprise. Although many chemical elements can serve as the central atom of Lewis acids, nitrogen is usually associated with Lewis bases. Here, we report on the first example of robust and modifiable Lewis acids centered on the nitrogen atom, which provide stable and well-characterized adducts with various Lewis bases. On the basis of the reactivity of nitrogen Lewis acids, we prepared, for the first time, cyclic triazanes, a class of cyclic organic compounds sequentially bearing three all-saturated nitrogen atoms (N-N-N motif). Reactivity abilities of these N-Lewis acids were explained by theoretical calculations. Properties and future applications of nitrogen Lewis acids are intriguing.

High and Reversible Ammonia Uptake in Mesoporous Azolate Metal-Organic Frameworks with Open Mn, Co, and Ni Sites.

A series of new mesoporous metal-organic frameworks (MOFs) made from extended bisbenzenetriazolate linkers exhibit coordinatively unsaturated metal sites that are responsible for high and reversible uptake of ammonia. Isostructural Mn, Co, and Ni materials adsorb 15.47, 12.00, and 12.02 mmol of NH3/g, respectively, at STP. Importantly, these near-record capacities are reversible for at least three cycles. These results demonstrate that azolate MOFs are sufficiently thermally and chemically stable to find uses in recyclable sorption, storage, and potentially separation of chemically challenging and/or corrosive gases, especially when designed to exhibit a high density of open metal sites.

Coordination chemistry of N-heterocyclic nitrenium-based ligands.

Comprehensive studies on the coordination properties of tridentate nitrenium-based ligands are presented. N-heterocyclic nitrenium ions demonstrate general and versatile binding abilities to various transition metals, as exemplified by the synthesis and characterization of Rh(I) , Rh(III) , Mo(0) , Ru(0) , Ru(II) , Pd(II) , Pt(II) , Pt(IV) , and Ag(I) complexes based on these unusual ligands. Formation of nitrenium-metal bonds is unambiguously confirmed both in solution by selective (15) N-labeling experiments and in the solid state by X-ray crystallography. The generality of N-heterocyclic nitrenium as a ligand is also validated by a systematic DFT study of its affinity towards all second-row transition and post-transition metals (Y-Cd) in terms of the corresponding bond-dissociation energies.

Nitrenium ions as ligands for transition metals.

Unlike N-heterocyclic carbenes (NHCs), which are now used ubiquitously in metal-based chemistry, the nitrogen-derived analogue (in which a carbon is replaced with the isoelectronic nitrogen cation, a nitrenium ion) has remained elusive as a ligand for metals. This is especially intriguing, because several other main-group analogues of NHCs have been prepared, and have been shown to coordinate with transition-metal complexes. Here, we describe the preparation of several N-heterocyclic nitrenium ions that are isoelectronic and isostructural to NHCs, and study their ligand properties. The formation of relatively strong nitrenium-metal bonds is unambiguously confirmed, in solution by selective (15)N-labelling experiments, and in the solid state by X-ray crystallography. Experimental and computational studies of the electronic properties of this novel type of ligand suggest that they are poor σ-donors and good π-acceptors.