Coordination Complexes of Ph3Sb2+ and Ph3Bi2+: Beyond Pnictonium Cations

The syntheses of salts containing ligand‐stabilized Ph₃Sb²⁺ and Ph₃Bi²⁺ dications have been realized by in situ formation of Ph₃Pn(OTf)₂ (Pn=Sb or Bi) and subsequent reaction with OPPh₃, dmap and bipy. The solid‐state structures demonstrate diversity imposed by the steric demands and nature of the ligands. The synthetic method has the potential for broad application enabling widespread development of the coordination chemistry for Pn^V acceptors.     

Cyclometalated Gold(III) Complexes: Synthesis,Reactivity, and Physicochemical Properties

This Review showcases the ability of bi‐ and tridentate ligands to stabilize gold in high oxidation states through the formation of mono‐ and biscyclometalated gold(III) complexes. In‐depth studies on the synthesis, intrinsic reactivity, catalytic relevance, and photophysical properties of stabilized gold(III) species have been carried out, setting the stage for exciting developments in various research areas, such as catalysis, inorganic and bioinorganic chemistry, ligand design, and materials science.     

Front Cover: Steric Influence on the Constitution of Beryllium Phosphine Complexes (Eur. J. Inorg. Chem. 29/2023)

The phosphine complexes of beryllium chloride, bromide and iodide, [(PMe₂Ph)₂BeX₂], [(PMePh₂)₂BeX₂] and [(PPh₃)BeX₂]₂ (X=Cl, Br, I) were prepared and characterised with multinuclear NMR spectroscopy. Additionally the molecular structure of dinuclear [(PPh₃)BeCl₂]₂ was determined with single crystal X-ray diffraction techniques. The threshold cone angle of the phosphines, below which two ligands can coordinate to the beryllium dihalide fragments, is between 136° and 145°. Halide-chloride exchange in dichloromethane is observed for [(PPh₃)BeBr₂]₂ and [(PPh₃)BeI₂]₂, which leads to the formation of [(PPh₃)BeCl₂]₂. Due to the relatively low Lewis basicity of PPh₃, it almost exclusively acts as a spectator ligand with only little formation of phosphonium cations.     

Establishing the Coordination Chemistry of Antimony(V) Cations: Systematic Assessment of Ph4Sb(OTf) and Ph3Sb(OTf)2 as Lewis Acceptors

The coordination chemistry of the stiboranes Ph₄Sb(OTf) ( 1 a , OTf = OSO₂CF₃) and Ph₃Sb(OTf)₂ ( 3 ) with Lewis bases has been investigated. The significant steric encumbrance of the Sb center in 1 a precludes interaction with most ligands, but the relatively low steric demands of 4‐methylpyridine‐N‐oxide (OPyrMe) and OPMe₃ enabled the characterization of [Ph₄Sb(OPyrMe)][OTf] ( 2 a ) and [Ph₄Sb(OPMe₃)][OTf] ( 2 b ), rare examples of structurally characterized complexes of stibonium acceptors. In contrast, 3 was found to engage a variety of Lewis bases, forming stable isolable complexes of the form [Ph₃Sb(donor)₂][OTf]₂ [donor=OPMe₃ ( 6 a ), OPCy₃ ( 6 b , Cy=cyclohexyl), OPPh₃ ( 6 c ), OPyrMe ( 6 d )], [Ph₃Sb(dmap)₂(OTf)][OTf] ( 6 e , dmap=4‐(dimethylamino)pyridine) and [Ph₃Sb(donor)(OTf)][OTf] [donor=1,10‐phenanthroline ( 7 a ) or 2,2′‐bipy ( 7 b , bipy=bipyridine)]. These compounds exhibit significant structural diversity in the solid‐state, and undergo ligand exchange reactions in line with their assignment as coordination complexes. Compound 3 did not form stable complexes with phosphine donors, with reactions instead leading to redox processes yielding SbPh₃ and products of phosphine oxidation.     

Oligo(borolyl)benzenes—Synthesis and Properties

Herein, we report the synthesis of boroles that are linked by a conjugated phenylene spacer. The characterization of these compounds was completed by NMR and UV/Vis spectroscopy, as well as X‐ray crystal diffraction. Furthermore, the coordination behavior of these oligoboroles towards five electronically and sterically disparate pyridine derivatives was studied and revealed fundamental differences in the properties of the resulting adducts. The experimental results were supported by density functional theory (DFT) calculations that showed a charge‐transfer effect upon formation of the pyridine‐4‐carbonitrile adduct. By chemical reduction of a tris(borolyl)‐substituted benzene derivative, a hexaanion was isolated as a result of a two‐electron reduction of each borolyl moiety. The interaction of the borolyl units through the aryl spacer, and the possible increase of the Lewis acidity due to the conjugation of the borolyl moieties, were investigated by base transfer reactions.     

Ru–η6‐Arene Cations [{(Ph2PC6H4)2B(η6‐Ph)}RuX]+ (X=Cl,H) as Lewis Acids

The reactivity of [{(Ph₂PC₆H₄)₂B(η⁶‐Ph)}RuCl][B(C₆F₅)₄] ( 1 ) as a Lewis acid was investigated. Treatment of 1 with mono and multidentate phosphorus Lewis bases afforded the Lewis acid–base adducts with the ortho‐carbon atom of the coordinated arene ring. Similar reactivity was observed upon treatment with N‐heterocyclic carbenes; however, adduct formation occurred at both ortho‐ and para‐carbon atoms of the bound arene with the para‐position being favoured by increased steric demands. Interestingly treatment with isocyanides resulted in adduct formation with the B‐centre of the ligand framework. The hydride‐cation [{(Ph₂PC₆H₄)₂B(η⁶‐Ph)}RuH] [B(C₆F₅)₄] was prepared via reaction of 1 with silane. This species in the presence of a bulky phosphine behaves as a frustrated Lewis pair (FLP) to activate H₂ between the phosphorus centre and the ortho‐carbon atom of the η⁶‐arene ring.     

Bis[N,N′‐diisopropylbenzamidinato(−)]silicon(II): Lewis Acid/Base Reactions with Triorganylboranes

Reaction of the donor‐stabilized silylene 1 (which is three‐coordinate in the solid state and four‐coordinate in solution) with BEt₃ and BPh₃ leads to the formation of the Lewis acid/base complexes 2 and 3 , respectively, which are the first five‐coordinate silicon compounds with an Si?B bond. These compounds were structurally characterized by crystal structure analyses and by multinuclear NMR spectroscopic studies in the solid state and in solution. Additionally, the bonding situation in 2 and 3 was analyzed by quantum chemical studies.     

Beryllium Complexes with Bio‐Relevant Functional Groups: Coordination Geometries and Binding Affinities

The coordination mode around beryllium in proteins and the binding affinity towards the peptide are unknown because there have been no coordination compounds of beryllium with ligands bearing bio‐relevant functional groups. We report the first comprehensive study on Be complexes with monodentate carboxylic acids, esters, aldehydes, and alcohols. Through solution and solid‐state techniques we determined that the binding affinities of Be²⁺ ions towards the functional groups are: carboxylate > alcohol > aldehyde > ester. Crystal structures of all the compounds have been determined including the unprecedented dodeca‐nuclear macrocyclic ring structure of non‐basic beryllium benzoate, which is the first example of those beryllium carboxylates. These findings enable the evaluation of potential beryllium binding sites inside proteins and is required to understand the mechanism of metal‐triggered immune responses.     

Synthesis and Reactivity of Molybdenum and Tungsten Alkyne Complexes Containing 6-Methylpyridine-2-thiolate Ligands

A series of M(II) and M(IV) (M=Mo, W) alkyne adducts employing two 6-methylpyridine-2-thiolate (6-MePyS) ligands was synthesized and investigated towards the nucleophilic attack of PMe₃ on the coordinated alkynes. For this approach, 2-butyne (C₂Me₂), phenylacetylene (HC₂Ph), and diphenylacetylene (C₂Ph₂) were used. For the exploration of an intramolecular attack, but-3-yn-1-ol (HCCCH₂CH₂OH) was coordinated to the metal centers. A nucleophilic attack of PMe₃ was observed in [W(CO)(HC₂Ph)(6-MePyS)₂] yielding an η²-vinyl compound. Reaction of [W(CO)(C₂Ph₂)(6-MePyS)₂] with excess PMe₃ resulted in the selective coordination of one molecule of PMe₃ concomitant with decoordination of the nitrogen atom of one 6-MePyS ligand. In contrast, the W(IV) complexes did not react with PMe₃. While no selectivity was observed in the reaction of the Mo(II) compounds with PMe₃, alkynes in the Mo(IV) compounds were replaced by PMe₃. Addition of Et₃N to the but-3-yn-1-ol complexes did not lead to the anticipated formation of 2,3-dihydrofuran.     

Synthesis,Structure, and Reactivity of Anionic sp2–sp3 Diboron Compounds: Readily Accessible Boryl Nucleophiles

Lewis base adducts of tetra‐alkoxy diboron compounds, in particular bis(pinacolato)diboron (B₂pin₂), have been proposed as the active source of nucleophilic boryl species in metal‐free borylation reactions. We report the isolation and detailed structural characterization (by solid‐state and solution NMR spectroscopy and X‐ray crystallography) of a series of anionic adducts of B₂pin₂ with hard Lewis bases, such as alkoxides and fluoride. The study was extended to alternative Lewis bases, such as acetate, and other diboron reagents. The B(sp²)–B(sp³) adducts exhibit two distinct boron environments in the solid‐state and solution NMR spectra, except for [(4‐tBuC₆H₄O)B₂pin₂]^?, which shows rapid site exchange in solution. DFT calculations were performed to analyze the stability of the adducts with respect to dissociation. Stoichiometric reaction of the isolated adducts with two representative series of organic electrophiles—namely, aryl halides and diazonium salts—demonstrate the relative reactivities of the anionic diboron compounds as nucleophilic boryl anion sources.     

Reactivity Studies of Iridium Pyridylidenes [TpMe2Ir(C6H5)2(C(CH)3C(R)NH] (R=H,Me, Ph)

The reactivity of a series of iridium? pyridylidene complexes with the formula [Tp^Me2Ir(C₆H₅)₂(C(CH)₃C(R)N H] ( 1 a – 1 c ) towards a variety of substrates, from small molecules, such as H₂, O₂, carbon oxides, and formaldehyde, to alkenes and alkynes, is described. Most of the observed reactivity is best explained by invoking 16 e^? unsaturated [Tp^Me2Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H₂ is heterolytically split to give hydride? pyridylidene complexes, whilst CO, CO₂, and H₂C?O provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five‐membered metallacycles with an IrCH₂CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four‐membered iridacycles with the IrC(?CH₂)N moiety. C₆H₅(C?O)H and C₆H₅C?CH react with formation of Ir? C₆H₅ and Ir? C?CPh bonds and the concomitant elimination of a molecule of pyridine and benzene, respectively. Finally the reactivity of compounds 1 a – 1 c against O₂ is described. Density functional theory calculations that provide theoretical support for these experimental observations are also reported.     

Insights on the Lewis Superacid Al(OTeF5)3: Solvent Adducts,Characterization and Properties**

Preparation and characterization of the dimeric Lewis superacid [Al(OTeF₅)₃]₂ and various solvent adducts is presented. The latter range from thermally stable adducts to highly reactive, weakly bound species. DFT calculations on the ligand affinity of these Lewis acids were performed in order to rank their remaining Lewis acidity. An experimental proof of the Lewis acidity is provided by the reaction of solvent-adducts of Al(OTeF₅)₃ with [PPh₄][SbF₆] and OPEt₃, respectively. Furthermore, their reactivity towards chloride and pentafluoroorthotellurate salts as well as (CH₃)₃SiCl and (CH₃)₃SiF is shown. This includes the formation of the dianion [Al(OTeF₅)₅]²⁻.