Przemyslaw Jan Malinowski

The first crystalline Cu(I)-Xe complex, Xe-Cu[Al(OR ^F ) ₄ ], 1 , (R ^F  = C(CF ₃ ) ₃ ), forms as a salt of the weakly coordinating perfluorinated alkoxyaluminate upon ligand exchange between elemental xenon and Cu(I)-N ₂ complex, Cu(N ₂ )[Al(OR ^F ) ₄ ]. Despite the lack of relativistic character of the copper ion, 1 is obtained under ambient Xe pressure and at room temperature. The crystal structure reveals that it is a molecular compound where xenon is a terminal ligand to copper with steric factors causing a Cu-Xe bond elongation in comparison with known gas-phase Xe-Cu(I) species. Extensive computational analysis facilitates the interpretation of spectral properties and gives insight into the nature of the bond between Xe and Cu[Al(OR ^F ) ₄ ]. EDA-NOCV and NPA indicate that electrostatic forces between Xe and Cu[Al(OR ^F ) ₄ ] have the largest share of its energy, though orbital interactions between the 5p orbital of Xe and the hybridized 4s/3d orbital of Cu as well as dispersive forces are also significant. Though the Xe-Cu[Al(OR ^F ) ₄ ] bond is fairly weak in comparison with Au ⁺ -Xe in the known [Xe-AuAsF ₃ ] complex, the isolation of 1 is possible thanks to the use of the weakly coordinating anion and solvent, which are worse ligands to copper than Xe atom.

While fully fluorinated alkoxyaluminates like [Al{OC(CF ₃ ) ₃ } ₄ ] ₋ have enabled multiple groundbreaking discoveries in the chemistry of highly reactive or unstable cations, their partially fluorinated congeners, particularly [Al{OCH(CF ₃ ) ₂ } ₄ ] ⁻ have proven more suitable for some applications, like electrochemistry or ionic salts. Despite the fact, the simplest and most basic salts (i.e. Li-Cs and Ag) of these partially fluorinated alkoxyaluminates have not yet been synthesized and or thoroughly characterized. To fill the gap, this work presents a thorough study of basic M(I) salts of [Al{OCH(CF ₃ ) ₂ } ₄ ] ⁻ and [Al{OC(CH ₃ )(CF ₃ ) ₂ } ₄ ] ⁻ for M = Li-Cs and Ag, including synthetic protocols, crystal structure determination, assessment of thermal stability and solubility in various organic solvents together with spectral characterization (IR, NMR). The obtained results show the vast variability of properties like crystal structure, solubility and thermal stability induced by seemingly minor changes in the structure of alkoxyaluminate anions. Additionally, structures of selected solvates with acetonitrile and products of partial hydrolysis of [Al{OCH(CF ₃ ) ₂ } ₄ ] ⁻ are discussed.

The reaction between anthracenes and N‐substituted maleimides was the first example for which the catalytic effect of AlCl ₃ on Diels–Alder reactions was shown. The current article presents a combined experimental and theoretical (DFT) study that extends the scope of accessible cycloadducts and also quantifies the influence of AlCl ₃ on reaction barrier and regioselectivity for a broad scope of reagents and different catalyst ratios. DFT calculations indicate that each aluminum trichloride bound to maleimide lowers the activation energy by ≈15–30 kJ mol ⁻¹ in reactions with anthracenes or naphthalenes. Moreover, calculations point to steric factors and not reaction barrier heights as the most relevant to the formation of anti‐ 1,4 isomers in cycloaddition reactions to 9,10‐dihaloanthracenes. Additionally, the inertness of 9‐cyanoanthracene can be ascribed to its high binding energy to AlCl ₃ .

While fully fluorinated alkoxyaluminates like [Al{OC(CF ₃ ) ₃ } ₄ ] ^- have enabled multiple groundbreaking discoveries in the chemistry of highly reactive or unstable cations, their partially fluorinated congeners, particularly [Al{OCH(CF ₃ ) ₂ } ₄ ] ^- have proven more suitable...

The title compound, [Ti(C ₄ F ₉ O) ₂ (C ₂ H ₃ N) ₄ ][Al(C ₄ F ₉ O) ₄ ] or [Ti{OC(CF ₃ ) ₃ } ₂ (CH ₃ CN) ₄ ][Al{OC(CF ₃ ) ₃ } ₄ ], is the first structurally characterized complex of Ti ^III containing four acetonitrile molecules and perfluorinated alkoxyaluminate in its coordination sphere. The [Ti{OC(CF ₃ ) ₃ } ₂ (CH ₃ CN) ₄ ] ⁺ cation adopts a compressed octahedral geometry where acetonitrile occupies the equatorial positions with apically bound alkoxide anions.

Nuclear magnetic resonance spectroscopy (NMR) is one of the most potent analytical chemistry methods, providing unique insight into molecular structures. Its noninvasiveness makes it a perfect tool for monitoring chemical reactions and determining their products and kinetics. Typically, the reactions are monitored by a series of ¹H NMR spectra acquired at regular time intervals. Even such a straightforward approach, however, often suffers from several problems. In particular, the reaction may cause sample inhomogeneity, resulting in a nonhomogenous magnetic field and distorted spectral lineshapes. When the studied process is fast, hardware correction (shimming and locking) cannot be applied on the fly, and the spectral quality degrades over the course of the reaction. Moreover, when nondeuterated solvents have to be used in the reaction mixture, a magnetic field-stabilizing system (deuterium lock) cannot work. Consequently, the spectra have distorted lineshapes, reduced resolution, and randomly varying peak positions, making them challenging to analyze quantitatively with standard software. In this paper, we propose a conceptually new approach to the quantitative analysis of a series of distorted spectra. The method is based on the Wasserstein distance and can effectively quantify the components of a reaction mixture without the need for peak-picking. We provide open-source software requiring minimum input from the user, i.e., a set of spectra indexed by time.

Wir stellen die Synthese und vollständige Charakterisierung des Kupfer‐Distickstoff‐Komplexes [(η¹‐N₂)Cu{Al(OR^F)₄}] 2 (R^F=C(CF₃)₃) vor, welcher durch eine Kaskaden‐Metathese‐Reaktion zwischen Ag[Al(OR^F)₄] und einem CuI‐Überschuss in iso‐Perfluorhexan (i‐pfh) unter N₂‐Atmosphäre hergestellt wurde. Die Titelverbindung 2 weist eine außerordentlich hohe N₂‐Streckschwingungsfrequenz von 2313/2314 cm⁻¹ (IR/Raman) auf und wurde durch Einkristall‐ und Pulver‐Röntgendiffraktometrie charakterisiert. Quantenchemische Ladungsverschiebungsanalysen basierend auf natürlichen Orbitalen der chemischen Valenz (CD‐NOCV) legen nahe, dass die Kupfer‐Distickstoff‐Interaktion durch eine schwache π‐Rückbindung charakterisiert wird, welche jedoch im Vergleich zu allen literaturbekannten Übergangsmetall‐Distickstoff‐Komplexen stark abgeschwächt ist.

We report the synthesis and full characterization of the copper dinitrogen complex [(η¹‐N₂)Cu{Al(OR^F)₄}] 2 (R^F=C(CF₃)₃) prepared by a cascade metathesis reaction of Ag[Al(OR^F)₄] with CuI‐excess in iso‐perfluorohexane (i‐pfh) under N₂ atmosphere. Title compound 2 features an extraordinarily high N₂ stretching frequency at 2313/2314 cm⁻¹ (IR/Raman) and was characterized by single‐crystal and powder X‐ray diffractometry. Quantum chemical charge displacement analysis based on natural orbitals of chemical valence (CD‐NOCV) indicates that the copper‐dinitrogen interaction is still governed by weak π‐backdonation, but is significantly reduced compared to all literature‐known transition metal dinitrogen complexes.