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Monitoring helical twists and effective molarities in dinuclear triple-stranded lanthanide helicates

The replacement of terminal benzimidazole-pyridine binding units in the neutral di-tridentate segmental ligand L1 with phenanthroline in L10 reduces the number of torsional degrees of freedom by two units. Reactions of these ligands with trivalent europium or lutetium cations yield structurally similar self-assembled dinuclear triple-stranded [Ln₂(Lk)₃]⁶⁺ complexes, thus demonstrating that the increased rigidity of the strand in L10 is compatible with its helical twist. With the larger lanthanum cations, the metallic coordination spheres are completed with two terminal axial triflate counter-anions to give [La₂(L10)₃(CF₃SO₃)₂]⁴⁺. Thermodynamic investigations in acetonitrile confirm the minor constraints produced by the planar phenanthroline unit in L10 leading to comparable effective molarities EMEu,L1 ≈ EMEu,L10 = 10-3.9(4) M with mid-range EuIII cations. The striking minute effective molarities EMLn,Ln-2H ≈ 10⁻⁶-10⁻⁹ M obtained upon the replacement of terminal phenanthrolines with structurally analogous fused hydroxyquinolines in L9 can be thus unambiguously assigned to solvation effects, a new tool for controlling complexity in metal-induced self-assembly processes.

Oxalic Amidines – Protonation Studies and Activity in Lactide Polymerisation

AbstractThe oxalic amidine N,N′‐dimethyl‐N,N′‐diphenyl‐1,2‐bis[4‐tolylimino]ethane‐1,2‐diamine was used to synthesise a chloridozinc complex and two monoprotonated species either with chloride or triflate counterions. The compounds have been structurally characterised by X‐ray crystallography. Proton affinities have been determined by quantum chemical calculations to investigate why only the iminium protonated species is selectively formed upon mild protonation. To better understand the coordination properties of the ligand, different possible coordination modes of the ligand to zinc chloride have been investigated by DFT calculations. The chloridozinc complex was applied as a catalyst in the melt polymerisation of rac‐lactide and exhibited high activity combined with excellent agreement between the obtained and calculated molecular weights.

An Iron(II) Complex of a Diamine-Bridged Bis-N-Heterocyclic Carbene

A diamine-bridged bis-N-heterocyclic carbene ligand was synthesized as imidazolium salts with chloride or triflate counteranions. Deprotonation of the chloride salt by an iron bis-amide complex or addition of the free diamine-bis-carbene ligand to FeCl2 led to the formation of an Fe(II) dichloride complex having a diamine-bis-carbene ligand, in which the iron atom is in a highly distorted octahedral geometry with weak Fe-N interactions. This iron complex was found to catalyze the hydrosilylation of acetophenone.

Liquid crystalline guanidinium phenylalkoxybenzoates: towards room temperature liquid crystals via bending of the mesogenic core and the use of triflate counter ions

A series of guanidinium salts 1(C n ) m –4(C n ) m X bearing phenyl alkoxybenzoate cores have been synthesised and their mesomorphic properties have been investigated by polarising optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction experiments (small-angle X-ray scattering and wide-angle X-ray scattering). While compounds 1(C12)1 X and 3(C12)1 X with one alkoxy chain showed smectic A (SmA) phases irrespective of the counter ion, compounds 1(C12)2 OTf and 3(C12)2 OTf with two alkoxy chains displayed SmA phases and the corresponding chlorides 1(C12)2 Cl and 3(C12)2 Cl displayed Colh. Guanidinium salts 1(C n )3–4(C n )3 X with three alkoxy chains showed Colh phases. Whereas the use of cyclic guanidinium head groups rather than acyclic ones had only a minor influence on the mesophase properties, melting points were significantly decreased by bent core units instead of linear core units. Replacement of chloride counterions by triflate lead to a further depression of the clearing points and shifted the mesophase towards room temperature.

Physicochemical properties of 1,2,3-triazolium ionic liquids

Ionic liquids composed of four different 1,2,3-triazolium cations with tosylate or triflate counter anions have been synthesized and characterized. Physicochemical properties of these ionic liquids including ion cluster behavior, thermal properties, electrochemical stability and ionic conductivity were determined and compared to corresponding imidazolium based ionic liquids. The impact of structure variations, in terms of substituents on the ring of the 1,2,3-triazolium cation and identity of the anion (i.e. tosylate versus triflate) is discussed. Stability of the 1,2,3-triazolium salts towards hydroxide ion at 80 °C was studied. Key features of 1,2,3-triazolium salts are their high electrochemical stability and ionic conductivity, comparable to imidazolium ionic liquids, but better chemical stability under alkaline conditions.

Tetrapyrrole cation receptor for selective binding fluoride ion

The 5,10,15,20-tetraphenyl-2,3,7,8,12,13,17,18,21,22,23,24-dodecamethylporphyrin ditriflate was synthesized and its complexing properties toward fluoride ion were investigated by spectrophotometric titration in the acetonitrile-tetrabutylammonium fluoride system. We found that at the complexation the two triflate counterions are replaced by the fluoride ions. The stability constants of the complexes and the concentration ranges of their existence were determined.

Synthesis and Properties of Metal–Ligand Complexes with Endohedral Amine Functionality

A series of tetracationic M(2)L(4) palladium-pyridyl complexes with endohedral amine functionality have been synthesized. The complexes were analyzed by NMR techniques (including Diffusion NMR and 2D NOESY), electrospray ionization (ESI) mass spectrometry, and X-ray crystallography. The solid state analysis shows a large change in crystal morphology upon introduction of the endohedral amine groups, caused by deleterious interactions between the amines and the triflate counterions from the coordination process. Combination of different ligands allows analysis of ligand exchange rates via NMR analysis, with half-lives on the order of 3 h, independent of the donor properties of the ligand. Self-sorting behavior is observed, with more electron-rich ligands being favored. The amine-containing and extended complexes are strongly fluorescent, giving quantum yields of up to 83%.

Multimetallic compounds containing cyclometalated Ir(III) units: Synthesis, structure, electrochemistry and photophysical properties

The reaction of the cyclometalated Ir III dimer [{(ppy) 2Ir} 2(μ-Cl) 2] (ppyH = 2-phenylpyridine) with silver triflate followed by a multidentate ligand [1,4-bis[3-(2-pyridyl)pyrazolylmethyl]benzene (bppb), 1,3,5-tri[3-(2-pyridyl)pyrazolylmethyl]-2,4,6-trimethylbenzene (tppb), 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz), 2-chloro-4,6-bis(dipyridin-2-ylamino)-1,3,5-triazine (cddt) or 2,4,6-tris(dipyridin-2-ylamino)-1,3,5-triazine (tdat)] afforded di- or trinuclear compounds: [{Ir(ppy) 2} 2(μ-bppb)](OTf) 2 ( 1), [{Ir(ppy) 2} 3(μ-tppb)](OTf) 3 ( 2), [{Ir(ppy) 2} 2(μ-tptz-OH)](OTf) ( 3), [{Ir(ppy) 2} 2(μ-cddt)](OTf) 2 ( 4) and [{Ir(ppy) 2} 2(μ-tdat)](OTf) 2 ( 5). All of these compounds contain cationic metal cores with corresponding triflate counter anions. The molecular structures of 1– 4 reveal that the structural feature of the Ir(ppy) 2 center of the starting precursor is conserved in the products. Also, because of the nature of the ligands, there is virtually no electronic communication between the Ir III centers except in 3 where a ring hydroxylation at the triazine carbon atom is effected upon metalation. Compounds 1– 5 are robust in solution where they retain their structural integrity. The UV–Vis and emission spectra of 1– 5 compounds are very similar to each other with the exception of 3 which seems to possess a different electronic structure. All the compounds are luminescent at room temperature. The emission bands indicate significant contribution from 3LC. Increase in the number of ‘Ir(ppy) 2’ units does not have any effect on emission color.

Synthesis of mono- and di-[12]aneN3 ligands and study on the catalytic cleavage of RNA model 2-hydroxypropyl-p-nitrophenyl phosphate with their metal complexes

A series of mono- and di-[12]aneN(3) ligands 1-6, which contain different substituents on the coordinating backbone, different linkers between two [12]aneN(3) units and different N-methylation on the [12]aneN(3) units, have been synthesized and fully characterized. The catalytic activities of their metal complexes on the cleavage of RNA model phosphate 2-hydroxypropyl-p-nitrophenyl phosphate (HPNPP) varied with the structures of the ligands and metal ions. Click reactions afforded an efficient method to prepare a series of [12]aneN(3) ligands, however, the incorporation of triazole moieties reduced the catalytic activities due to their coordination with metal ions and the strong inhibition from the triflate counter ion. Dinuclear zinc(II) complexes containing an m-xylyl bridge showed higher catalytic activities with synergistic effects up to 700-fold. Copper(II) complexes with the ligands without triazole moieties proved to be highly reactive and showed strong cooperativity between the two copper(II) ions. In terms of k(2), dinuclear complexes Zn(2)-3b, Zn(2)-3d, Zn(2)-4b, and Cu(2)-4b afforded activities of 7.9 × 10(5), 3.9 × 10(4), 9.0 × 10(4), and 8.1 × 10(4)-fold higher than that of methoxide. The ortho arrangement of the two [12]aneN(3) units and the presence of 5- or 2-positioned substituents in the benzene ring as well as N-methylation of [12]aneN(3) units greatly reduced the catalytic activities due to the steric effects. These results clearly indicate that the structures of the linker between two [12]aneN(3) units play very important role in their catalytic synergistic effects.

Influence of Hydrogen Bonds on the Stability of Some Cationic Monoaminocarbene Tantalum Complexes Containing Tridentate Bis(phenolato) [OSO]-Type Ligands

A series of new cationic aminocarbene tantalum complexes have been synthesized and characterized. A significant contribution of the anion−cation interaction to the stability of the cationic moiety has been revealed. The complexes with a triflate or chloride counterion are very stable, even in air, while the corresponding tetraphenylborate derivatives are very unstable species. This stabilizing behavior can be explained by the establishment of hydrogen bonds between the electronegative atoms of the anion and the amine and hydroxyl protons of the cation. The presence of the hydrogen bonds has been detected by spectroscopic and structural techniques.

(S)-4-tert-Butyl-2-phenyl-2-oxazoline derived palladacycles as efficient catalysts for the decomposition of P=S pesticides

Three palladacycles with N,N-trans coordination, (S)-{2-[2-(4-tert-butyl)oxazolinyl]phenyl-C1,N}(4-R-pyridine)(aqua) n palladium(II) triflate (R = CF3, n = 1, 1; R = H, n = 0, 2; R = NMe2, n = 1, 3), have been prepared from the respective chloride precursors and were characterized with IR and 1H-NMR and elemental analyses. The crystal structures of 2 and a pincer complex (S,S)-{2,6-bis[2-(4-iso-propyl)oxazolinyl]phenyl-N,C1,N}bromo-palladium(II) hydrate (5) were determined. For methanolysis of P=S pesticides, it was found that ortho-palladated complexes 1–3 effectively catalyzed the reaction; however, the pincer complex 4 with triflate counterion was much less active. Relative to the methoxide-promoted background reaction at 10.80, 1 mmol L−1 of palladacycles 1–3 can accelerate the methanolysis by 8.7 × 109, 1.5 × 109, and 1.0 × 108-fold, respectively. For racemic P=S pesticides, such as letophos and EPN, it proved that there is no clear chiral discrimination during the catalysis. The reaction mechanism of the catalytic methanolysis was discussed according to the experimental results.

Supramolecular Structure, Thermal and Spectroscopic Properties of a New Coordination Polymer: Catena-Bis(μ2-4,4′-dipyridyldisulfide-κ2N,N′)-Bis(AQUO)-Copper(II)di-trifluoromethanesulfonate

A new supramolecular network of copper (II), [{Cu(bpds)2(H2O)2}] • 2CF3SO3]n, (I), (bpds = 4,4′-bipyridildisulfide) has been synthesized and characterized by elemental analysis and Fourier transform infrared (FT-IR) and its structure determined using X-ray crystallography. The thermal decomposition mechanism of the complex was studied by using thermogravimetry-derivative thermogravimetry (TG-DTG) techniques. X-ray structural analysis revealed that the coordination polymer displays 1D chains. The octahedral O2N4 chromophore surrounding the metal ion forms via two trans located water oxygen and four nitrogen from four bpds ligand. The structure consists of Cu(H2O)2 fragments linked by pairs of bpds ligand to form a double-stranded chain. The thermogravimetric analysis indicates sequential loss of adsorbed and coordinated water and triflate counter ion, prior to more comprehensive ligand fragmentation at elevated temperatures.

Mechanism of a Chemical Glycosylation Reaction

Glycosylation is arguably the most important reaction in the field of glycochemistry, yet it involves one of the most empirically interpreted mechanisms in the science of organic chemistry. The beta-mannopyranosides, long considered one of the more difficult classes of glycosidic bond to prepare, were no exception to this rule. A number of logical but circuitous routes for their preparation were described in the literature, but they were accompanied by an even greater number of mostly ineffective recipes with which to access them directly. This situation changed in 1996 with the discovery of the 4,6-O-benzylidene acetal as a control element permitting direct entry into the beta-mannopyranosides, typically with high yield and selectivity. The unexpected nature of this phenomenon demanded study of the mechanism, leading first to the demonstration of the alpha-mannopyranosyl triflates as reaction intermediates and then to the development of alpha-deuterium kinetic isotope effect methods to probe their transformation into the product glycosides. In this Account, we assemble our observations into a comprehensive assessment consistent with a single mechanistic scheme. The realization that in the glucopyranose series the 4,6-O-benzylidene acetal is alpha- rather than beta-directing led to further investigations of substituent effects on the stereoselectivity of these glycosylation reactions, culminating in their explanation in terms of the covalent alpha-glycosyl triflates acting as a reservoir for a series of transient contact and solvent-separated ion pairs. The function of the benzylidene acetal, as explained by Bols and co-workers, is to lock the C6-O6 bond antiperiplanar to the C5-O5 bond, thereby maximizing its electron-withdrawing effect, destabilizing the glycosyl oxocarbenium ion, and shifting the equilibria as far as possible toward the covalent triflate. beta-Selective reactions result from attack of the nucleophile on the transient contact ion pair in which the alpha-face of the oxocarbenium ion is shielded by the triflate counterion. The alpha-products arise from attack either on the solvent-separated ion pair or on a free oxocarbenium ion, according to the dictates of the anomeric effect. Changes in selectivity from varying stereochemistry (glucose versus mannose) or from using different protecting groups can be explained by the shifting position of the key equilibria and, in particular, by the energy differences between the covalent triflate and the ion pairs. Of particular note is the importance of substitutents at the 3-position of the donor; an explanation is proposed that invokes their evolving torsional interaction with the substituent at C2 as the chair form of the covalent triflate moves toward the half-chair of the oxocarbenium ion.

Correlations Between Nucleophilicities and Selectivities in the Substitutions of Tetrahydropyran Acetals

Selectivities that deviate from S(N)1 stereoelectronic models in the nucleophilic substitutions of tetrahydropyran acetals were investigated. When weak nucleophiles were employed, stereoselectivities conformed to known S(N)1 stereoelectronic models. In contrast, stereoselectivities in the substitutions of acetals with strong nucleophiles depended on reaction conditions. Erosions in selectivities were observed when strong nucleophiles were employed in the absence of coordinating counterions. These erosions in selectivities are attributed to rates of nucleophilic additions to oxocarbenium ion intermediates that approach the diffusion limit. When triflate counterions were present, however, S(N)2-like pathways became accessible with strong nucleophiles. In most cases examined, the major stereoisomers formed from reactions that proceeded through S(N)2-like pathways were opposite to the major stereoisomers formed from the analogous reactions that proceeded through S(N)1 pathways.

Equatorial Anomeric Triflates from Mannuronic Acid Esters

Activation of mannuronic acid esters leads to a conformational mixture of alpha-anomeric triflates, in which the equatorial triflate ((1)C(4) chair) is formed preferentially. This unexpected intermediate clearly opposes the anomeric effect and is mainly stabilized by the electron-withdrawing carboxylate function at C-5. Because the anomeric center carries a significant positive charge, the (1)C(4) mannopyranosyl chair approximates the favored (3)H(4) half-chair oxacarbenium ion conformation. The excellent beta-selectivity in glycosylations of mannuronates is postulated to originate from the cooperative action of the triflate counterion and the (stereo)electronic effects governing oxacarbenium ion stabilization in the transition state leading to the 1,2-cis product.

A DFT study on the mechanism of a novel, regioselective, intramolecular N–π rearrangement of cis and trans-η1-N-Cp*Rh-hydroxytamoxifen complexes to their η6 derivatives; potential breast cancer pharmaceuticals, and fluorescent probes

The previously reported reactions of cis and trans-hydroxytamoxifen drug derivatives, 1 and 2, with [Cp*Rh(L)(3)](2+) complexes (L = H(2)O, CH(3)OH), initially provided the kinetically controled eta(1)-N complexes, 4(OTf, CH(3)OH) and 5(OTf, CH(3)OH), which underwent a novel, intramolecular, regioselective N-pi rearrangement to provide the eta(6) complexes, 6 and 7. A dramatic solvent effect was also observed on the rate of this N-pi rearrangement in CH(3)OH or CH(2)Cl(2). Therefore, a DFT study was conducted that provided further mechanistic and thermodynamic data on this N-pi rearrangement. The preferred structures of both the eta(1)-N and eta(6) complexes in the two solvents were determined, and a thorough analysis of their geometries and electronic structures has been provided. The influence of the solvent on the N-pi rearrangement was studied by including the solvent both implicitly using a PCM model, and explicitly by introducing the counterion and/or the solvent molecules into the inner and outer coordination spheres of the complexes. It was shown that the triflate (OTf(-)) counterion was strongly bound in the inner coordination sphere of the eta(1)-N complexes, 4(OTf) and 5(OTf), and in the outer sphere of the coordinatively saturated eta(6) complexes, 6 and 7, especially in non-polar media. The cleavage of the ionic Cp*Rh-OTf bond was found to be the rate-limiting step in the N-pi rearrangement. The thermodynamic results suggested that the eta(6) complexes were more stable than the eta(1)-N complexes in CH(2)Cl(2) and in CH(3)OH at elevated temperatures. The opposite relationship for the stabilities of the eta(1)-N complexes was found in CH(3)OH at room temperature, thus corroborating the experimental results that the N-pi rearrangement did not occur, under these conditions. A plausible mechanistic pathway for the N-pi rearrangement was proposed from our extensive DFT studies, that included several important intermediates and transition states, and provided a unique view of this novel transformation.

Vicinal diphosphoniums: electrostatic repulsion under covalent constraint

A series of five vicinal bis(alkyl-triarylphosphoniums) derived from o-bis(diphenyl-phosphino)benzene (o-dppb) is described. Each of them have been prepared by specific methods, and their formal electrostatic and possible van der Waals strain is compared through the P+...P+ distances in the crystal state. According to X-ray diffraction analyses, while the conformations of the dimethyl dication is C2 symmetric, the conformation of alka-1,n-diyl-diphosphoniums (n = 1, 2, 3) is pseudo-Cs symmetric. The solution structure of the dimethyldiphosphonium 2 was studied by NMR techniques after metathesis of the triflate counterions with enantiomerically pure X-PHAT chiral anions (X = TRIS, BIN). [(Delta)-BINPHAT] was indirectly shown to discriminate between the enantiomers of the diphosphonium, but no effective enantio-differentiation could be measured down to -70 degrees C in CD2Cl2. When associated to [(Delta)-TRISPHAT] counterions, progressive cleavage of the diphosphonium afforded the corresponding methyl-triphenyl-monophosphonium salt. In the bridged series, the diphosphoniacyclopentene dication was found to be stable in spite of the very short transannular P+...P+ distance (2.83 A). The naturally more relaxed homologous diphosphoniacyclohexene dication (P+...P+ = 3.28 A) was found to be flexible in solution, as indicated by the equivalence of the four protons of the +P-CH2CH2-P+ bridge from 20 degrees C to -80 degrees C in acetone-d6. The two diphosphoniacycloheptene dications exhibit no P+...P+ steric compression (ca 3.64 A), just as the dimethyl dication (3.70 A). In solution, the seven-membered ring of the +P-CH2CR2CH2-P+ dications (R = H, Me) remains rigidly Cs symmetric: no interconversion of the pseudo-axial and pseudo-equatorial R groups is evidenced at the NMR time scale at -95 degrees C (coalescence at -20 degrees C for R = H, at -65 degrees C for R = Me). According to DFT calculations at the B3PW91/6-31G** level in 1,2-dichloroethane (DCE: PCM, epsilon = 10.36), the lowest energy conformation is indeed Cs-symmetric. However a quasi-isoenergetic C2-symmetric conformation which is the most stable in the gas phase is also found, and is thus a likely intermediate in the observed Cs <==> Cs interconversion. This +P-CH2CMe2CH2-P+ diphosphonium was obtained by dialkylation of o-dppb with 2,2-dimethylpropan-1,3-diyl bistriflate in DCE at 80 degrees C. The use of this solvent was the key for the synthesis of this dication, which was however competitively produced along with some +P-CH2CH2-P+ dication. The latter was also obtained by a totally different route, by heating a sulfinylethyl monophosphonium salt of o-dppb in the presence of the cationic complex [Rh(cod)2][PF6]. A mechanism for this peculiar process is proposed.

Dimanganese and Diiron Complexes of a Binucleating Cyclam Ligand: Four-Electron, Reversible Oxidation Chemistry at High Potentials

The reaction of a binucleating biscyclam ligand cyclam(2)(i)PrO [where cyclam(2)(i)PrO = (1,3-bis[1,4,8,11-tetraazacyclododecane]-2-hydroxypropane] with Mn(CF(3)SO(3))(2) or Fe(CF(3)SO(3))(2).2MeCN gives [(cyclam(2)(i)PrO)Mn(2)(mu-CF(3)SO(3))](CF(3)SO(3))(2) (4) and [(cyclam(2)(i)PrO)Fe(2)(mu-CF(3)SO(3))](CF(3)SO(3))(2) (6), respectively. [(cyclam(2)(i)PrO)Mn(2)(mu-N(3))](CF(3)SO(3))(2) (5) is obtained by the reaction of 4 with NaN(3). Single-crystal X-ray structural characterization indicates that in each of the bimetallic complexes the two metal centers are facially coordinated by a cyclam ligand and bridged by the isopropoxide linker of the ligand in addition to a triflate counteranion. Upon replacement of the triflate bridge with the single-atom bridge of an end-bound azide ligand in 5, the Mn-Mn distance decreases by 0.38 A. All of the complexes are high-spin and colorless and were characterized by magnetic susceptibility measurements, electron paramagnetic resonance spectroscopy, and electrochemical methods. Magnetic susceptibility measurements indicate that 4 and 6 are weakly antiferromagnetically coupled while 5 is weakly ferromagnetically coupled. Cyclic voltammetry measurements indicate that the hard donor amine ligands impart high oxidation potentials to the metal centers and that four-electron redox activity can be accessed with a narrow potential range of 0.72 V. Upon inclusion of water in the cyclic voltammetry experiment, the oxidative waves shift to higher potentials, which is consistent with water binding the manganese centers. The diiron complex 6 displays four one-electron redox couples, of which the final two are irreversible. Inclusion of water in the cyclic voltammetry measurement for compound 6 resulted in two sets of shifted peaks, which suggests that two molecules of water bind the diiron core. In accordance with the observed reversibility of the electrochemical results, the dimanganese complex is more efficient than the diiron complex for mediating O-atom transfer to organic substrates and is an excellent hydrogen peroxide disproportionation catalyst, with the reaction proceeding for over 20,000 turnovers.

Oxygen Donor-Mediated Equilibration of Diastereomeric Alkene−Palladium(II) Intermediates in Enantioselective Desymmetrizing Heck Cyclizations

This investigation examines the origin of enantioselection in the desymmetrization of an acyclic prochiral Heck cyclization precursor. High asymmetric induction (97-98% ee) is attributed to a temporary interaction of a Lewis basic oxygen donor with weakly Lewis acidic palladium(II). A series of control experiments combined with quantum-chemical model calculations provided sound evidence for a mechanism involving oxygen donor-mediated, rapid equilibration of diastereomeric alkene-palladium(II) complexes prior to the selectivity-determining ring-closing event, a Curtin-Hammett scenario. Our study also highlights the importance of the cationic pathway (triflate counter anions versus halido ligand) and alkene stereochemistry (E versus Z) in asymmetric Heck reactions.

Cationic Main Group Element Cages of Germanium(II) and Tin(II) Consisting of 3,5‐Di(t‐butyl) Substituted Pyrazolyl Ligands in the Bridging Position

AbstractThe transamination reaction of [Ge{N(SiMe3)2}2] with two equivalents of 3,5‐di(t‐butyl)pyrazole H(3,5‐tBu2pz) yielded the homoleptic germanium(II) pyrazolyl compound 4. Treatment of 4 and its analogous tin(II) compound 1 with triflic acid (HOTf) in diethyl ether afforded cationic, triply pz‐bridged cages of the general formula [E(μ2‐3,5‐tBu2pz)3E]+OTf− (E = Ge 5, Sn 6) in good yields. The sterically demanding t‐butyl substituted μ2‐pyrazolyl bridges adopt a skew arrangement with respect to the E···E vector in the solid state. DFT calculations were performed on the cage compounds 5 and 6 in order to elucidate the influence of the tilting of the pyrazolyl ligands as well as a weak coordination of the triflate counter anion in 6 on the intramolecular element element distances within the cationic moieties.