Frustrated Lewis pairs (FLPs) have a great potential for activation of small molecules. Most known FLP systems are based on boron or aluminum atoms as acid functions, few zinc, and only two boron-isoelectronic silicenium cation systems. The first system neutral silane, (C2F5)3SiCH2P(tBu)2 (1), was prepared from (C2F5)3SiCl with C2F5 groups very high electronegativity LiCH2P(tBu)2. 1 is capable cleaving hydrogen, adds CO2 SO2. Hydrogen splitting confirmed by H/D scrambling reactions....

Abstract Tris[tetrafluoro‐4‐(trifluoromethyl)phenyl]borane (BTolF) was prepared by treating boron tribromide with tetrameric F 3 CC 6 4 ‐Cu I . The generated from MgBr and copper(I) bromide. Lewis acidities of BTolF evaluated the Gutmann–Beckett method calculated fluoride‐ion affinities are 9 10 %, respectively, higher than that tris(pentafluorophenyl)borane (BCF) even SbF 5 molecular structures BCF were determined gas‐phase electron diffraction, also single‐crystal X‐ray diffraction.

The covalent diamantyl (C28H38) and oxadiamantyl (C26H34O2) dimers are stabilized by London dispersion attractions between the dimer moieties. Their solid-state gas-phase structures were studied using a multitechnique approach, including single-crystal X-ray diffraction (XRD), electron (GED), combined GED/microwave (MW) spectroscopy study, quantum chemical calculations. inclusion of medium-range correlation as well energy in density functional theory is essential to reproduce experimental...

The geminal frustrated Lewis pair (FLP) (F5 C2 )3 SnCH2 P(tBu)2 (2) was prepared by reacting SnCl with LiCH2 . It is neutral and contains an extremely electronegatively substituted, but relatively soft (hard-soft acid-base, HSAB) acidic tin function. Its FLP-type reactivity proven reaction a variety of small molecules (CO2 , SO2 CS2 PhNCO, HCl, (Ph3 P)AuCl). However, it shows no in H/D scrambling experiments H2 /D2 mixtures binds CO2 reversibly, as observed VT-NMR spectroscopy. Compound 2...

Catechols occupy a unique role in the structural, bio-, and geochemistry of silicon. Although wealth knowledge exists on their hypercoordinate complexes, structure tetracoordinate bis(catecholato)silane, Si(catH)2 1, has been enigmatic since its first report 1951. Indeed, claim planar-tetracoordinated silicon 1 triggered prominent debate, which is unsettled to this day. Herewith, we present comprehensive structural study derivatives gas phase by electron diffraction, neon matrix IR...

Abstract A bidentate pnictogen bonding host‐system based on 1,8‐diethynylanthracene was synthesized by a selective tin‐antimony exchange reaction and investigated regarding its ability to act as Lewis acidic host component for the complexation of basic or anionic guests. In this work, novel C≡C−Sb(C 2 F 5 ) unit established study potential antimony(III) sites representatives scarcely explored donors. The capability partly fluorinated system towards halide anions (Cl − , Br I ), dimethyl...

Abstract A bidentate boron Lewis acid based on 1,8‐diethynylanthracene has been studied in detail with respect to its adduct formation diamines and diphosphanes of different linker lengths between the donor functions. clear correlation length bifunctional base 1 : adducts, 2 adducts or oligomers was found. The were characterized solution by NMR titration experiments structurally X‐ray diffraction. In addition, competition host system ZR 3 (Z=N, P; R=H, Me) demonstrated generally higher...

Structures of molecules in the gas phase, determined experimentally, provide definitive information about their identity, reactivity and other properties, free from intermolecular interactions. Available methods have not been applicable to large asymmetric molecules. Now SARACEN (Structure Analysis Restrained by Ab initio Calculations for Electron diffractioN) method, using data computational complement experimental data, has opened door full structure determination all sufficiently volatile

Oxygenation reactions of dialkylzinc solutions have been investigated. Me2Zn reacts with oxygen in the absence water to give bis(heterocubane) [(MeZn)6Zn(OMe)8], whereas Et2Zn and iPr2Zn afford mono(heterocubanes) [(RZn)4(OR)4]. In presence small amounts (added during or after oxygenation) product types are reversed for giving [(MeZn)4(OMe)4] [(EtZn)6Zn(OEt)8], while being retained (giving [(iPrZn)4(OiPr)4]). Full characterization all products by NMR spectroscopy, mass spectrometry,...

Abstract The formation of host–guest (H‐G) complexes between 1,8‐bis[(diethylgallanyl)ethynyl]anthracene (H) and the N‐heterocycles pyridine pyrimidine (G) was studied in solution using a combination NMR titration diffusion experiments. For latter, coefficients potential structures were compared with those tailor‐made reference compounds similar shape (synthesized characterized by NMR, HRMS, part XRD). Highly dynamic behavior observed both cases, but different species equilibria. With...

Chlorogermane (C2 F5 )3 GeCl with very electronegative pentafluoroethyl groups was converted LiCH2 P(tBu)2 to obtain the intramolecular frustrated Lewis pair (FLP) GeCH2 , a neutral, germanium-based FLP. Its reactivity compared its silicon homologue SiCH2 . Both FLPs cleave NO but give cyclic (Si) and open-chain oxides (Ge). In reactions HCl both gave same adduct type in solid state, while proton seems more mobile solution germanium case. Reactions PhCNO Me3 SiCHN2 result ring-type adducts....

This work combines halogen and chalcogen bonding. Short, polarity directed C–X⋅⋅⋅Ch (X = Br or I, Ch Se Te) contacts were prepared by in situ low‐temperature cocrystallization of liquid mixtures neutral pentafluorohalogenobenzenes C6F5X dimethyl chalco­genides Me2Ch. Solid‐state structures Me2Se Me2Te determined 150 125 years after their first description. Significant C–Ch⋅⋅⋅Ch make dimeric polymeric. The cocrystals comprise C6F5X⋅⋅⋅Me2Ch⋅⋅⋅XC6F5 aggregates, except the combination X/Ch I/Te...

The composition of the saturated vapors two platinum com­plexes with macrocyclic ligands 5,10,15,20‐tetraphenyl­porphyrin (PtTPP) and 5,10,15,20‐tetrakis(pentafluoro­phenyl)­por­phyrin (PtTF5PP) their structures were determined by syn­chronous gas‐phase electron diffrac­tion/mass spectrometry (GED/MS). These porphyrin are those heaviest metal atom in coordination cavity that have been structurally investigated gas phase. mass spectra confirm presence a single molecular form each, PtTPP...

Semi‐flexible bidentate Lewis acids based on the biphe­nylene backbone were synthesized by selective anti‐Markownikow hydroborations using dicyclohexylborane. In addition, initial host‐guest chemistry experi­ments carried out comple­xation of monodentate bases PMe3 and pyridine, as well biden­tate pyrimidine bis(dimethylphosphanyl­methyl)­dime­thyl­silane (BisPhos). The BisPhos is found to undergo a che­la­te‐type comple­xation, whereas complexed in different manner forming 1:2 adduct...

Perfluoropropionic acid (CF₃CF₂C(O)OH) will be investigated with a focus on its complex structural properties. As formal derivative of propanoic acid, the incorporation fluorine atoms imparts unique features, including three distinct monomeric conformations and dimeric structure. This study presents experimental findings, supported by computational modeling, to explore these characteristics. The analysis includes an FTIR isolated species in Ar-cryogenic matrix low-temperature determination...

A synthetic route to flapping poly-Lewis acids (PLAs) based on dibenzocyclooctatetra­ene was developed. The reactivity of tetradentate boron and aluminium containing PLAs towards various Lewis bases (LB) including drugs was...

Tetrakis(N,N-dimethylhydroxylamido)silane, Si(ONMe2)4 (1), and the analogous ethyl compound, Si(ONEt2)4 (2), have been prepared by reaction of silicon tetrachloride with 4 equiv corresponding lithium N,N-dialkylhydroxylamide. The compounds characterized elemental analysis, IR spectroscopy, NMR spectroscopy nuclei 1H, 13C, 15N [including determination 1J(29Si15N) coupling constants], 17O, 29Si, nominal high-resolution mass spectrometry. A crystal structure on 1 showed molecule to be (4 +...

(F3C)F2SiONMe2 was prepared from LiONMe2 and F3CSiF3. It characterized by gas IR multinuclear solution NMR spectroscopy mass spectrometry. Its structure elucidated single crystal X-ray crystallography electron diffraction. (It exists as a conformer mixture.) Important findings were extremely acute SiON angles [solid 74.1(1)°, anti 84.4(32)° gauche 87.8(20)°] short Si···N distances 1.904(2) Å]. The bending potential of the unit calculated at MP2/6-311++G(3df,2dp) level theory appears very...

The molecular and electronic structures of AsP(3) P(4) have been investigated. Gas-phase electron diffraction studies provided r(g) bond lengths 2.3041(12) 2.1949(28) A for the As-P interatomic distances P-P distances, respectively. gas-phase structure has redetermined provides an updated value 2.1994(3) reconciling conflicting literature values. photoelectron spectroscopy experimental values energies ionizations from valence orbitals shows that electronically are quite similar. Solid-state...

The reaction of 1,3,5-trimethyl-1,3,5-triazacyclohexane (TMTAC) with [La{Al(CH3)4}3] resulted in C–H activation, leading to the formation [(TMTAC)La{Al(CH3)4}{(μ3-CH2)[Al(CH3)2(μ2-CH3)]2}] (1) containing a bis(aluminate) dianion and subsequent extrusion methane. A similar [Y{Al(CH3)4}3] led CH4, [TMTAC{Al(CH3)3}2] (2) {[(TMTAC)Y][Y2(μ2-CH3)][{(μ6-C)[Al(μ2-CH3)2(CH3)]3}{(μ3-CH2)(μ2-CH3)Al(CH3)2}2] (3), six-coordinate carbide ion two [CH2Al(CH3)3]2− anions. Compound 3 is product multiple...

Graphical Abstract An Improved Gas Electron Diffractometer – The Instrument, Data Collection, Reduction and Structure Refinement Procedures

Abstract Lithium carbenoids are versatile compounds for synthesis owing to their intriguing ambiphilic behavior. Although this class of has been known several years, few solid‐state structures exist because high reactivity and often low thermal stability. Using cryo X‐ray techniques, we were now able elucidate the first structure a Li/F alkyl carbenoid, pentafluoroethyllithium (LiC 2 F 5 ), finally yielding prototype investigating structure—reactivity relationships molecules. The compound...

Starting from ferrocene, pentafluoroferrocene [Fe(C5F5)(C5H5)] can be prepared in five steps via a one-pot lithiation-electrophilic fluorination strategy. Pentafluoroferrocene was characterized by multinuclear NMR and IR spectroscopy, cyclovoltammetry as well X-ray (solid) electron diffraction (gas) the experimental results compared with DFT calculations.

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(N,N-Dimethylaminoxy)trifluorosilane, F3SiONMe2 (1), was prepared by the reaction of LiONMe2 with SiF4 in Me2O at −96 °C as a colorless, air-sensitive liquid, which identified gas-phase IR spectroscopy and NMR nuclei 1H, 13C, 15N, 17O, 19F, 29Si. The geometry 1, determined electron diffraction analysis refined Cs symmetry, is influenced weak attractive interactions between Si N: Si···N 2.273(17) Å, Si−O−N 94.3(9)°, [Si−O 1.619(8) N−O 1.479(7) O−Si−Fin-plane 104.1(10)°, O−Si−Fout-of-plane...