Why Are Some Pnictogen(III) Pincer Complexes Planar and Others Pyramidal?

Geometrically-constrained pnictogen pincer complexes have emerged in recent years as platforms for unique stoichiometric and catalytic chemical transformations. These complexes feature dynamic conformations ranging from fully planar at the pnictogen centre to distorted-pyramidal geometries, as well as variation between phases. Although the valued reactivity of pnictogen pincer complexes is ascribed to their geometries, there is no unified model to explain the observed conformational outcomes across different ligands and pnictogen centres. Here we propose such a model through computational analysis of more than 1300 structures across 64 complexes (16 ligands and 4 heavy pnictogens), explaining the experimental observations and making new predictions. By looking at signatures of bond stability (bond lengths, Wiberg bond indices) and delocalization (NPA charges, Hirshfeld charges), our framework posits a pnictogen-based σ-bonding effect that favours pyramidalization and exists in competition with a ligand-based π-bonding effect that favours planarity. Variations in structure as a function of pnictogen identity, ligand tethering, electronics, and aromaticity can be reconciled with reference to a balance between these two opposing forces. Careful consideration of the σ/π-bonding effects may aid in the rational design of future pnictogen pincer complexes with predictable geometries and reactivities.

Substitution Lability of the Perfluorinated Cp* Ligand in [Rh(COD)(C5(CF3)5)] Towards Triphenylpnictogens EPh3 (E=N, P, As, Sb, Bi).

Triphenylpnictogens EPh3 (E=N, P, As, Sb, Bi) are able to displace the perfluorinated Cp* ligand in [Rh(COD)(C5(CF3)5)] (COD=1,5-cyclooctadiene) in up to quantitative yield. The resulting ionic products contain [C5(CF3)5]- as uncoordinated counter anion. The cations feature [Rh(COD)]+ fragments, coordinated by one (N, Bi), two (P, As) or three (Sb) triphenylpnictogen moieties. Whereas coordination via the pnictogen is observed for P, As and Sb, π-coordination of the aryl rings is observed for N and Bi.

Light-Dependent Reactivity of Heavy Pnictogen Double Bonds.

The chemistry of light dipnictenes has been widely investigated in the last century with remarkable achievements especially for azobenzene derivatives. In contrast, distibenes and dibismuthenes are relatively rare and show very limited reactivity. Herein, we have designed a protocol using visible light to enhance the reactivity of heavy dipnictenes. Exploiting the distinctive π-π* transition, we have been able to isolate unique examples of dipnictene-cobalt complexes. The reactivity of the distibene complex was further exploited using red light in the presence of a diazoolefin to access an unusual four-membered bicyclo[1.1.0]butane analog, containing only a single carbon atom. These findings set the bases to a conceptually new strategy in heavy element double bonds chemistry where visible light is at the front seat of bond activation.

Frustrated Lewis Pair Chelation in the p-Block.

Frustrated Lewis pairs (FLPs) have been the subject of considerable study since the field's inception. While much of the research into FLPs has centered around small molecule activation for diverse stoichiometric and catalytic transformations, intramolecular FLPs also show promise as chelating ligands. The cooperative action of Lewis basic and acidic moieties enables intramolecular FLPs to stabilize low oxidation state centers and (consequently) reactive molecular fragments through a donor-acceptor approach, making them an attractive ligand class in main group element chemistry. This review outlines the state of FLP chelation to date throughout the p-block, encompassing primarily groups 13-16.

Binding, Release and Functionalization of Intact Pnictogen Tetrahedra Coordinated to Dicopper Complexes.

The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu2 (µ,η1 : η1 -MeCN)][X]2 (X=weakly coordinating anion, NTf2 (1 a), FAl[OC6 F10 (C6 F5 )]3 (1 b), Al[OC(CF3 )3 ]4 (1 c)) was replaced by white phosphorus (P4 ) or yellow arsenic (As4 ) to yield [(DPFN)Cu2 (µ,η2 : η2 -E4 )][X]2 (E=P (2 a-c), As (3 a-c)). The molecular structures in the solid state reveal novel coordination modes for E4 tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E4 tetrahedra. Reactions with N-heterocyclic carbenes (NHCs) led to replacement of the E4 tetrahedra with release of P4 or As4 and formation of [(DPFN)Cu2 (µ,η1 : η1 -Me NHC)][X]2 (4 a,b) or to an opening of one E-E bond leading to an unusual E4 butterfly structural motif in [(DPFN)Cu2 (µ,η1 : η1 -E4 Dipp NHC)][X]2 (E=P (5 a,b), E=As (6)). With a cyclic alkyl amino carbene (Et CAAC), cleavage of two As-As bonds was observed to give two isomers of [(DPFN)Cu2 (µ,η2 : η2 -As4 Et CAAC)][X]2 (7 a,b) with an unusual As4 -triangle+1 unit.

Synthesis of Tetrahedranes Containing the Unique Bridging Hetero-Dipnictogen Ligand EE' (E ≠ E'=P, As, Sb, Bi).

In order to improve and extend the rare class of tetrahedral mixed main group transition metal compounds, a new synthetic route for the complexes [{CpMo(CO)2 }2 (µ,η2 :η2 -PE)] (E=As (1), Sb (2)) is described leading to higher yields and a decrease in reaction steps. Via this route, also the so far unknown heavier analogues containing AsSb (3 a), AsBi (4) and SbBi (5) ligands, respectively, are accessible. Single crystal X-ray diffraction experiments and DFT calculations reveal that they represent very rare examples of compounds comprising covalent bonds between two different heavy pnictogen atoms, which show multiple bond character and are stabilised without any organic substituents. A simple one-pot reaction of [CpMo(CO)2 ]2 with ME(SiMe3 )2 (M=Li, K; E=P, As, Sb, Bi) and the subsequent addition of PCl3 , AsCl3 , SbCl3 or BiCl3 , respectively, give the complexes 1-5. This synthesis is also transferable to the already known homo-dipnictogen complexes [{CpMo(CO)2 }2 (µ,η2 :η2 -E2 )] (E=P, As, Sb, Bi) resulting in higher yields comparable to those in the literature reported procedures and allows the introduction of the bulkier and better soluble Cp' (Cp'=tert butylcyclopentadienyl) ligand.

Pnictogen-Functionalised C1 Ligands: MC-ARn (n=0, 1, 2, 3).

The chemistry of transition metal carbynes, Ln M≡CR, has historically been dominated by species bearing hydrocarbyl or amino 'R' substituents, with other elements appearing only sporadically. In recent years, carbynes and related 'C1 ' species bearing other main-group substituents, particularly heavier elements of the p-block, have begun to emerge. This review details the chemistry of heavier pnictogen-functionalised C1 ligands, MCARn (A=P, As, Sb, Bi; n=0-3), including their syntheses, properties and reactivities, and how these are distinguished from more traditional carbyne complexes. Recent developments in the closely related phospha-isonitrile Ln M(CPR), cya-phosphide and cya-arside ligands, Ln M(C≡A) (A=P, As), are also discussed.

Uncovering the Hidden Landscape of Tris(4-pyridyl) Ligands: Topological Complexity Derived from the Bridgehead.

Supramolecular main group chemistry is a developing field which parallels the conventional domain of metallo-organic chemistry. Little explored building blocks in this area are main group metal-based ligands which have the appropriate donor symmetry to build desired molecular or extended arrangements. Tris(pyridyl) main group ligands (E(py)3 , E=main group metal) are potentially highly versatile building blocks since shifting the N-donor arms from the 2- to the 3-positions and 4-positions provides a very simple way of changing the ligand character from mononuclear/chelating to multidentate/metal-bridging. Here, the coordination behaviour of the first main group metal tris(4-pyridyl) ligands, E(4-py)3 (E=Sb, Bi, Ph-Sn) is explored, as well as their ability to build metal-organic frameworks (MOFs). The complicated topology of these MOFs shows a marked influence on the counter anion and on the ability of the E(4-py)3 ligands to switch coordination mode, depending on the steric and donor character of the bridgehead. This structure-directing influence of the bridgehead provides a potential building strategy for future molecular and MOF design in this area.

Isolation and Structural Determination of a Hexacoordinated Antimony(V) Dication.

The hexacoordinated antimony(V) dication [(ppy)3 Sb]2+ ([1]2+ ; ppy=2-(2-pyridyl)phenyl), stabilized by three intramolecular donor-acceptor interactions, has been isolated as its hexachloroantimonate salt [1][SbCl6 ]2 , prepared by the oxidative addition of chlorine to the neutral stibine [(ppy)3 Sb] (1), followed by the abstraction of chloride. Air-stable [1][SbCl6 ]2 exhibits remarkable thermal stability and the three ppy ligands on the antimony atom are shown to be magnetically inequivalent in the 1 H and 13 C NMR spectra. A hexacoordinated, meridional octahedral bonding geometry has been determined for [1][SbCl6 ]2 by X-ray crystallographic analysis. Theoretical calculations were performed to investigate why the meridional form was generated preferentially over the facial form. In addition, the dynamics of the ppy ligands were investigated by variable-temperature 1 H NMR spectroscopy. The potential to generate dications by using a single-electron-transfer reagent has also been investigated. The dication [1]2+ is the first [12-Sb-6]2+ chemical species to have been structurally determined.

Two-dimensional inorganic nanosheets: production and utility in the development of novel electrochemical (bio)sensors and gas-sensing applications.

This review (with 178 references) focuses on inorganic layered materials (ILMs) and the use of their two-dimensional nanosheets in the development of novel electrochemical (bio)sensors, analytical devices, and gas-phase sensing applications. The text is organized in three main sections including the presentation of the most important families of ILMs, a comprehensive outline of various "bottom-up", "top-down," and hydro(solvo)thermal methods that have been used for the production of ILM nanosheets, and finally an evaluative survey on their utility for the determination of analytes with interest in different sectors of contemporary analysis. Critical discussion on the effect of the production method on their electronic properties, the suitability of each nanomaterial in different sensing technologies along with an assessment of the performance of the (bio)sensors and devices that have been proposed within the last 5 years, is enclosed. The perspectives of further improving the utility of 2D inorganic nanosheets in sensing applications, in real-world samples, are also discussed.

Pnictogens Allotropy and Phase Transformation during van der Waals Growth.

With their ns2 np3 valence electronic configuration, pnictogens are the only system to crystallize in layered van der Waals (vdW) and quasi-vdW structures throughout the group. Light pnictogens crystallize in the A17 phase, and bulk heavier elements prefer the A7 phase. Herein, we demonstrate that the A17 of heavy pnictogens can be stabilized in antimonene grown on weakly interacting surfaces and that it undergoes a spontaneous thickness-driven transformation to the stable A7 phase. At a critical thickness of ∼4 nm, A17 antimony transforms from AB- to AA-stacked α-antimonene by a diffusionless shuffle transition followed by a gradual relaxation to the A7 phase. Furthermore, the competition between A7- and A17-like bonding affects the electronic structure of the intermediate phase. These results highlight the critical role of the atomic structure and substrate-layer interactions in shaping the stability and properties of layered materials, thus enabling a new degree of freedom to engineer their performance.

Bismuth Amides Mediate Facile and Highly Selective Pn-Pn Radical-Coupling Reactions (Pn=N, P, As).

The controlled release of well-defined radical species under mild conditions for subsequent use in selective reactions is an important and challenging task in synthetic chemistry. We show here that simple bismuth amide species [Bi(NAr2 )3 ] readily release aminyl radicals [NAr2 ]. at ambient temperature in solution. These reactions yield the corresponding hydrazines, Ar2 N-NAr2 , as a result of highly selective N-N coupling. The exploitation of facile homolytic Bi-Pn bond cleavage for Pn-Pn bond formation was extended to higher homologues of the pnictogens (Pn=N-As): homoleptic bismuth amides mediate the highly selective dehydrocoupling of HPnR2 to give R2 Pn-PnR2 . Analyses by NMR and EPR spectroscopy, single-crystal X-ray diffraction, and DFT calculations reveal low Bi-N homolytic bond-dissociation energies, suggest radical coupling in the coordination sphere of bismuth, and reveal electronic and steric parameters as effective tools to control these reactions.

Hetero Diels-Alder Reactions of Masked Dienes Containing Heavy Group†15 Elements.

Treatment of N,C,N-chelated organopnictogen(I) compounds ArE (1-3) (Ar=2,6-(RN=CH)2 C6 H3 , E/R=As/Dmp (1), Sb/tBu (2), and Bi/tBu (3), where Dmp=2,6-Me2 C6 H3 ) with various electron-deficient alkynes RC≡CR' (R/R'=CO2 Me (DMAD), R/R'=H/CO2 Me, or R/R'=NC5 F4 ) affords different types of heterocyclic compounds. In these reactions, 1-3 act as hidden dienes and participate in hetero-Diels-Alder (DA) reactions, a feature that has been only rarely reported for heavier pnictogen compounds. In this way, reactions of 1 furnished the set of 1-arsanaphthalenes 4-6. The most likely mechanism involves two steps, that is, an arsa-DA reaction giving a 1-arsa-1,4-dihydro-iminonaphthalene, followed by CH→NH proton migration. In contrast, this reaction sequence terminates at the first step in the case of the antimony analogue 2, thus giving the 1-stiba-1,4-dihydro-iminonaphthalenes 7 and 8. Reactions of the bismuth congener 3 gave one of two products depending on the alkyne used. Reaction of 3 with DMAD gave 1-bisma-1,4-dihydro-iminonaphthalene 9, whilst its reaction with two equivalents of HC≡C(CO2 Me) gave bismacyclohexadiene (10). All compounds have been characterized by NMR, IR, and Raman spectroscopies and X-ray diffraction analysis. The experimental data were complemented by a computational study, including a description of the reaction profiles of the hetero-DA reactions and an assessment of the aromaticities of the heterocyclic naphthalene derivatives.

Noncovalent Functionalization of Pnictogen Surfaces: From Small Molecules to 2D Heterostructures.

Beyond graphene, 2D pnictogen polymers are rapidly growing among the family of 2D materials. Due to their unique properties, this group has received considerable interest in recent years. Those properties include tunable electronic band gaps, high charge carrier mobility, and in-plane anisotropic properties. This Review covers the noncovalent functionalization of pnictogen surfaces considering experimental and theoretical studies. Noncovalent functionalization is of great importance for effective modulation of the electronic structure of these materials as well as improvement of their stability toward surface oxidation. This Review highlights their noncovalent modification by organic molecules, in which enhanced surface stability of phosphorene and generated functionalized materials for applications in biomedical, supercapacitors, energy storage, and biosensors. Moreover, the noncovalent interactions with small molecules show its significance for sensing applications. Lastly, the interactions of pnictogen sheets with other 2D materials and their applications for van der Waals heterostructure formation are discussed. Current state-of-the-art as well as future perspectives in this field are covered.

Donor Strengths Determination of Pnictogen and Chalcogen Ligands by the Huynh Electronic Parameter and Its Correlation to Sigma Hammett Constants.

The suitability and accuracy of the Huynh electronic parameter (HEP) was further tested to reveal remote substituent effects in pyridines, which are located five or six bonds away from the reporter probe. These values show an excellent correlation to Hammett σ-constants of the respective substituents with coefficients of R2 =0.9856 (σm ) and R2 =0.9857 (σp ). Based on this observation, a methodology for the re-evaluation of certain Hammett constants with larger uncertainties has been proposed and demonstrated. Moreover, the scope of HEP was extended to various neutral pnictogen and chalcogen donors during which "transphobia effects" were revealed for mixed NHC complexes containing phosphites, arsine and stibine for the first time.

Ring Expansions of Nonpolar Polyphosphorus Rings.

The reaction of the phosphinidene complex [Cp*P{W(CO)5 }2 ] (1 a) (Cp*=C5 Me5 ) with the anionic cyclo-Pn ligand complex [(η3 -P3 )Nb(ODipp)3 ]- (2, Dipp=2,6-diisopropylphenyl) resulted in the formation of [{W(CO)5 }2 {µ3 ,η3:1:1 -P4 Cp*}Nb(ODipp)3 ]- (3), which represents an unprecedented example of a ring expansion of a polyphosphorus-ligand complex initiated by a phosphinidene complex. Furthermore, the reaction of the pnictinidene complexes [Cp*E{W(CO)5 }2 ] (E=P: 1 a, As: 1 b) with the neutral complex [Cp'''Co(η4 -P4 )] (Cp'''=1,2,4-tBu3 C5 H2 ) led to a cyclo-P4 E ring (E=P, As) through the insertion of the pentel atom into the cyclo-P4 ligand. Starting from 1 a, the two isomers [Cp'''Co(µ3 ,η4:1:1 -P5 Cp*){W(CO)5 }2 ] (5 a,b), and from 1 b, the three isomers [Cp'''Co(µ3 ,η4:1:1 -AsP4 Cp*){W(CO)5 }2 ] (6 a-c) with unprecedented cyclo-P4 E ligands (E=P, As) were isolated. The complexes 6 a-c represent unique examples of ring expansions which lead to new mixed five-membered cyclo-P4 As ligands. The possible reaction pathways for the formation of 5 a,b and 6 a-c were investigated by a combination of temperature-dependent 31 P{1 H} NMR studies and DFT calculations.

Permethylated Disila[2]metallocenophanes of Group 14 and 15 Elements.

Permethylated disila[2]metallocenophanes of silicon, germanium, tin, lead, 2 a-d, (tetrelocenophanes) and antimony, 3 a,b, (pnictogenocenophanes) are described. In the case of antimony, a chloro-substituted stibonocenophane, 3 a, as well as cationic stibonocenophanium tetrachloroaluminate and tetraphenylborate salts, 3 b[X] (X=[AlCl4 ], [BPh4 ]), were synthesized. These represent the first examples of metallocenophanes of any Group 15 element. All compounds were studied in solution and in the solid state. Without exception the ansa-bridge exerts a strong influence on the bending angle of the two Cp-ligands. For disila[2]plumbocenophane, 2 d, its reactivity towards Group 15 halides was probed. Treatment of disila[2]plumbocenophane, 2 d, with two equivalents of phosphorus(III) chloride or arsenic(III) chloride, results in a ring-opening reaction and gives the bis(dihalopnictogenyl)-substituted products, 4 a,b.

Tricoordinate Nontrigonal Pnictogen-Centered Radical Anions: Isolation, Characterization, and Reactivity.

The search for main-group element-based radicals is one of the main research topics in contemporary chemistry because of their fascinating chemical and physical properties. The Group 15 element-centered radicals mainly feature a V-shaped two coordinate structure, with a couple of radical cations featuring trigonal tricoordinated geometry. Now, nontrigonal compounds R3 E (E=P, As, Sb) were successfully synthesized by introducing a new rigid tris-amide ligand. The selective one-electron reduction of R3 E afforded the first stable tricoordinate pnictogen-centered radical anion salts; the pnictogen atoms retain planar T-shaped structures. EPR spectroscopy and calculations reveal that the spin density mainly resides at the p orbitals of the pnictogen atoms, which is perpendicular to the N3 E planes.

Pnictogen-Based Enzymatic Phenol Biosensors: Phosphorene, Arsenene, Antimonene, and Bismuthene.

Two-dimensional materials have allowed for great advances in the biosensors field and to obtain sophisticated, smart, and miniaturized devices. In this work, we optimized a highly sensitive and selective phenol biosensor using 2D pnictogens (phosphorene, arsenene, antimonene, and bismuthene) as sensing platforms. Exfoliated pnictogen were obtained by the shear-force method, undergoing delamination and downsizing to thin nanosheets. Interestingly, compared with the other tested elements, antimonene exhibited the highest degree of exfoliation and the lowest oxidation-to-bulk ratio, to which we attribute its enhanced performance in the phenol biosensor system reported here. The proposed design represents the first biosensor approach developed using exfoliated pnictogens beyond phosphorene.

London Dispersion Interactions in Pnictogen Cations [ECl2 ]+ and [E=E]2+ (E=P, As, Sb) Supported by Anionic N-Heterocyclic Carbenes.

Several pnictogen dihalide complexes of the type (WCA-IDipp)EX2 (E=P, As, Sb; X=Cl, Br) that bear an anionic N-heterocyclic carbene ligand with a weakly coordinating borate moiety (WCA-IDipp, WCA=B(C6 F5 )3 , IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were prepared by salt metathesis reactions between the respective pnictogen trihalides EX3 and the lithium salt (WCA-IDipp)Li⋅toluene. Two-electron reduction of the dihalides (WCA-IDipp)EX2 with 1,3-bis(trimethylsilyl)-1,4-dihydropyrazine or elemental magnesium afforded the dipnictenes (WCA-IDipp)2 E2 , which display typical element-element double bonds as observed in diaryldiphosphenes, -arsenes and -stibenes. To provide an insight into the factors contributing to the structural stability of the pnictogen dihalide and dipnictene compounds, quantum chemical calculations were performed at the domain-based local pair natural orbital coupled-cluster (DLPNO-CCSD(T)) level. A local energy decomposition (LED) analysis of the interaction between the carbene and the pnictogen dihalide or dipnictene moiety demonstrates that London dispersion is an essential factor for the stabilization of these compounds.