A Highly Sterically Encumbered Boron Lewis Acid Enabled by an Organotellurium-Based Ligand.

Lewis acidic boron compounds are ubiquitous in chemistry due to their numerous applications, yet tuning and optimizing their properties towards different purposes is still a challenging field of research. In this work, the boron-based Lewis acid B[OTeF3(C6F5)2]3 was synthesized by reaction of the teflate derivative HOTeF3(C6F5)2 with BCl3 or BCl3 ⋅ SMe2. This new compound presents a remarkably high thermal stability up to 300 °C, as well as one of the most sterically encumbered boron centres known in the literature. Theoretical and experimental methods revealed that B[OTeF3(C6F5)2]3 exhibits a comparable Lewis acidity to that of the well-known B(C6F5)3. The affinity of B[OTeF3(C6F5)2]3 towards pyridine was accessed by Isothermal Titration Calorimetry (ITC) and compared to that of B(OTeF5)3 and B(C6F5)3. The ligand-transfer reactivity of this new boron compound towards different fluorides was demonstrated by the formation of an anionic Au(III) complex and a hypervalent iodine(III) species.

Formation of Peroxynitrite, [O-N-O-O]-, via a Cascade of Reactions between Ozonide and Ammonia.

We report on an unexpected reaction between ammonia and potassium ozonide dissolved in liq. NH3 resulting in the formation of peroxynitrite, [ONOO]-, which exclusively happens in the presence of a specific partially fluorinated aniline-based ammonium cation. High-resolution structural data of the peroxynitrite anion in cis-conformation have been obtained. We further studied this molecule anion by single crystal Raman spectroscopy. The cis and trans isomers of peroxynitrite were analysed computationally with respect to their relative energies, the cis-trans transition barrier and their decomposition pathways to the nitrate anion. By experimentally examining cations decorated with fluorine ligands to different degrees, we demonstrate that fluorine specific interactions play a crucial role in the unexpected formation of peroxynitrite and as a conspicuously structure directing factor for the underlying crystalline solid phases, exhibiting distinct micro-separations of fluorine and hydrogen enriched regions.

Trifluoromethyl Fluorosulfonate (CF3OSO2F) and Trifluoromethoxy Sulfur Pentafluoride (CF3OSF5) - Two Gaseous Sulfur(VI) Compounds with Insulating Properties.

In this work, we analyzed trifluoromethyl fluorosulfonate (CF3OSO2F) and trifluoromethoxy sulfur pentafluoride (CF3OSF5) regarding their potential use as dielectrics by investigating some of their intrinsic and extrinsic properties. Both compounds show a higher breakdown voltage than SF6 with averaged relative breakdown voltages of 1.3±0.2 for CF3OSO2F and 1.4±0.2 for CF3OSF5 compared to SF6 with 1.0. Like the dielectric (CF3)2CFCN, both compounds decompose during the breakdown process. The decomposition products were analyzed by IR spectroscopy and GCIR methods. Furthermore, the molecular structures of both gaseous compounds CF3OSO2F and CF3OSF5 have been determined by in situ crystallization, and their physical properties were determined as well.

Further Perspectives on the Teflate versus Fluoride Analogy: The Case of a Co(II) Pentafluoroorthotellurate Complex.

The pentafluoroorthotellurate group (teflate, OTeF5) is considered as a bulky analogue of fluoride, yet its coordination behavior in transition metal complexes is not fully understood. By reaction of [CoCl4]2- and neat ClOTeF5, we synthesized the first cobalt teflate complex, [Co(OTeF5)4]2-, which exhibits moisture-resistant Co-OTeF5 bonds. Through a combined experimental and theoretical (DFT and NEVPT2) study, the properties and electronic structure of this species have been investigated. It exhibits a distorted tetrahedral structure around the cobalt center and can be described as a d7 system with a quartet (S = 3/2) ground state. A comparative bonding analysis of the (pseudo)tetrahedral [CoX4]2- anions (X = OTeF5, F, Cl) revealed that the strength of the Co-X interaction is similar in the three cases, being the strongest in [Co(OTeF5)4]2-. In addition, an analysis of the charge of the Co center reinforced the similar electron-withdrawing properties of the teflate and fluoride ligands. Therefore, the [Co(OTeF5)4]2- anion constitutes an analogue of the polymeric [CoF4]2- in terms of electronic properties, but with a monomeric structure.

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 )3 SiCl and (CH3 )3 SiF is shown. This includes the formation of the dianion [Al(OTeF5 )5 ]2- .

Oxygen-Bridged Ga2 (Et)3 (OTeF5 )3 and the Weakly Coordinating Anions [Ga(Et)(OTeF5 )3 ]- and [Ga(OTeF5 )4 ].

Salts of the weakly coordinating anions [Ga(OTeF5 )4 ]- as well as [Ga(Et)(OTeF5 )3 ]- and the neutral Ga2 (Et)3 (OTeF5 )3 were synthesized and characterized by spectroscopic methods and single-crystal X-ray diffraction. Ga2 (Et)3 (OTeF5 )3 was formed by treating GaEt3 with pentafluoroorthotelluric acid (HOTeF5 ) and reacted with PPh4 Cl and CPh3 Cl to [PPh4 ][Ga(Et)(OTeF5 )3 ] and [CPh3 ][Ga(Et)(OTeF5 )3 ]. In contrast, Ag[Ga(OTeF5 )4 ] was prepared from AgOTeF5 and GaCl3 and was used as a versatile starting material for further reactions. Starting with Ag[Ga(OTeF5 )4 ] the substrates [PPh4 ][Ga(OTeF5 )4 ] and [CPh3 ][Ga(OTeF5 )4 ] were formed from PPh4 Cl and CPh3 Cl.

Taming the High Reactivity of Gold(III) Fluoride: Fluorido Gold(III) Complexes with N-Based Ligands.

The synthesis of [NMe4 ][AuF4 ] and [NEt4 ][AuF4 ], as well as an improved one-pot synthesis of Cs[AuF4 ], is reported. The new [AuF4 ]- salts were structurally characterized by single crystal X-ray diffraction, NMR spectroscopy, vibrational spectroscopy, and mass spectrometry. These salts are the first gold(III) fluoride salts that can be isolated in pure form and are convenient to be used in usual organic solvents for subsequent synthesis. The formation of molecular AuF3 complexes in solution is further reported, characterized as [F3 Au(NCCH3 )] at low temperature, as [F3 Au(py)] and a binuclear derivative which are stable at room temperature. The stability of these species in common organic solvents was investigated and they showed a satisfying stability.

Superacids Based on Pentafluoroorthotellurate Derivatives of Aluminum.

The new Lewis acid Al(OTeF5 )3 and its acetonitrile adduct CH3 CN→Al(OTeF5 )3 were obtained by a simple one-step synthesis in batches of up to 15 g. Al(OTeF5 )3 and the adduct were characterized by vibrational spectroscopy (IR, Raman) and quantum-chemical calculations. Furthermore, five different salts of the new weakly coordinating anion [Al(OTeF5 )4 ]- were prepared in a two-step procedure. [Ph4 P][Al(OTeF5 )4 ], Cs[Al(OTeF5 )4 ], [Ph3 C][Al(OTeF5 )4 ], as well as the protonated benzene derivatives [C9 H13 ][Al(OTeF5 )4 ] and [C6 H7 ][Al(OTeF5 )4 ] were characterized by low-temperature single-crystal X-ray diffraction and NMR spectroscopy. Arenium salts have rarely been characterized in the solid state and were synthesized in this work in a simplified fashion.

Structural Proof for the First Dianion of a Polychloride: Investigation of [Cl8 ](2.).

The polychloride salt [CCl(NMe2 )2 ](+) 2 [Cl8 ](2-) was synthesized and crystallized in the ionic liquid [BMP]OTf. The compound was fully characterized by Raman spectroscopy as well as X-ray single-crystal structure determination, and represents the first example of a polychloride dianion to be described. Detailed gas-phase and solid-state calculations concerning the nature of the bonding situation were also performed.

[Xe(OTeF5)(pyF)]+: a strong oxidizing xenonium(II) teflate cation with N-donor bases.

Herein we report on the formation of the adduct salts [Xe(OTeF5)(pyF)][Al(OTeF5)4] (pyF = C5F5N, C5H3F2N) by abstraction of an -OTeF5 group from Xe(OTeF5)2 with the Lewis superacid Al(OTeF5)3 and subsequent adduct formation of the generated [XeOTeF5]+ cation with fluorinated pyridines. These salts represent the first xenonium cations with the weakly coordinating [Al(OTeF5)4]- anion. The strong oxidizing property of these compounds is further assessed.

Questing for homoleptic mononuclear manganese complexes with monodentate O-donor ligands.

Compounds containing Mn-O bonds are of utmost importance in biological systems and catalytic processes. Nevertheless, mononuclear manganese complexes containing all O-donor ligands are still rare. Taking advantage of the low tendency of the pentafluoroorthotellurate ligand (teflate, OTeF5) to bridge metal centers, we have synthesized two homoleptic manganese complexes with monomeric structures and an all O-donor coordination sphere. The tetrahedrally distorted MnII anion, [Mn(OTeF5)4]2-, can be described as a high spin d5 complex (S = 5/2), as found experimentally (magnetic susceptibility measurements and EPR spectroscopy) and using theoretical calculations (DFT and CASSCF/NEVPT2). The high spin d4 electronic configuration (S = 2) of the MnIII anion, [Mn(OTeF5)5]2-, was also determined experimentally and theoretically, and a square pyramidal geometry was found to be the most stable one for this complex. Finally, the bonding situation in both complexes was investigated by means of the Interacting Quantum Atoms (IQA) methodology and compared to that of hypothetical mononuclear fluoromanganates. Within each pair of [MnXn]2- (n = 4, 5) species (X = OTeF5, F), the Mn-X interaction is found to be comparable, therefore proving that the similar electronic properties of the teflate and the fluoride are also responsible for the stabilization of these unique species.

Air-stable aryl derivatives of pentafluoroorthotellurate.

We report on two different sets of air-stable derivatives of pentafluoroorthotellurate containing fluorinated and non-fluorinated aryl groups. The acid cis-PhTeF4OH was obtained in gram scale and further transformed to Ag[cis-PhTeF4O], which was used as a cis-PhTeF4O transfer reagent to obtain [PPh4][cis-PhTeF4O]. Furthermore, the synthesis of trans-(C6F5)2TeF3OH was achieved by a selective hydrolysis of trans-(C6F5)2TeF4 in the presence of KF and subsequent protonation by aHF. Quantum-chemical calculations show a higher acidity and robustness against fluoride abstraction for trans-(C6F5)2TeF3OH compared to cis-PhTeF4OH.

Structural proof of a [C-F-C]+ fluoronium cation.

Organic fluoronium ions can be described as positively charged molecules in which the most electronegative and least polarizable element fluorine engages in two partially covalent bonding interactions to two carbon centers. While recent solvolysis experiments and NMR spectroscopic studies on a metastable [C-F-C]+ fluoronium ion strongly support the divalent fluoronium structure over the alternative rapidly equilibrating classical carbocation, the model system has, to date, eluded crystallographic analysis to confirm this phenomenon in the solid state. Herein, we report the single crystal structure of a symmetrical [C-F-C]+ fluoronium cation. Besides its synthesis and crystallographic characterization as the [Sb2F11]- salt, vibrational spectra are discussed and a detailed analysis concerning the nature of the bonding situation in this fluoronium ion and its heavier halonium homologues is performed, which provides detailed insights on this molecular structure.

[P4H]+[Al(OTeF5)4]-: protonation of white phosphorus with the Brønsted superacid H[Al(OTeF5)4](solv).

A sustainable transformation of white phosphorus (P4) into chemicals of higher value is one of the key aspects in modern phosphorus research. Even though the chemistry of P4 has been investigated for many decades, its chemical reactivity towards the simplest electrophile, the proton, is still virtually unknown. Based on quantum-chemical predictions, we report for the first time the successful protonation of P4 by the Brønsted acid H[Al(OTeF5)4](solv). Our spectroscopic results are in agreement with acid-mediated activation of P4 under protonation of an edge of the P4-tetrahedron and formation of a three-center two-electron P-H-P bond. These investigations are of fundamental interest as they permit the activation of P4 with the simplest electrophile as a new prototype reaction for this molecule.

Tuning the Lewis acidity of difluorido gold(iii) complexes: the synthesis of [AuClF2(SIMes)] and [AuF2(OTeF5)(SIMes)].

The synthesis and structural characterisation of the difluorido organo gold(iii) complexes [AuClF2(SIMes)] and [AuF2(OTeF5)(SIMes)] are presented. The substitution of a fluorido ligand in [AuF3(SIMes)] by an OTeF5 group increases the Lewis acidity of the Au moiety. A scale for carbene affinities is presented, which correlates calculated and experimental values for the Lewis acidity of the metal centre in akin compounds.