Inorganic Chemistry, Год журнала: 2023, Номер 62(37), С. 14828 - 14832
Опубликована: Сен. 7, 2023
We demonstrate the increased Lewis acidity on going from Sn(II) to Sn(IV) by oxidizing TpMe2SnOTf (OTf = SO3CF3) TpMe2SnF(OTf)2. Replacement of fluoride ion in TpMe2SnF(OTf)2 a triflate, resulting TpMe2Sn(OTf)3 further enhances at tin. 119Sn NMR spectroscopy, modified Gutmann-Beckett test, computational analysis, and catalytic phosphine oxide deoxygenation support claims.
Язык: Английский
Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(4)
Опубликована: Ноя. 10, 2021
IUPAC defines Lewis acidity as the thermodynamic tendency for pair formation. This strength property was recently specified global (gLA), and is gauged example by fluoride ion affinity. Experimentally, usually evaluated effect on a bound molecule, such induced
Язык: Английский
Процитировано
123
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(24)
Опубликована: Фев. 27, 2023
Key challenges in modern synthetic chemistry include the design of reliable, selective, and more sustainable methods, as well development promising candidates for new materials. Molecular bismuth compounds offer valuable opportunities they show an intriguing spectrum properties that is yet to be fully exploited: a soft character, rich coordination chemistry, availability broad variety oxidation states (at least +V -I) formal charges +3 -3) at Bi atoms, reversible switching between multiple states. All this paired with status non-precious (semi-)metal good tendency towards low toxicity. Recent findings some these only come into reach, or can substantially optimized, when charged are specifically addressed. In review, essential contributions synthesis, analyses, utilization ionic highlighted.
Язык: Английский
Процитировано
31
Journal of the American Chemical Society, Год журнала: 2023, Номер 145(36), С. 19458 - 19477
Опубликована: Авг. 30, 2023
Motivated by the discovery of main group Lewis acids that could compete or possibly outperform ubiquitous organoboranes, several groups, including ours, have engaged in chemistry acidic organoantimony compounds as new platforms for anion capture, sensing, and transport. Principal to this approach are intrinsically elevated properties antimony, which greatly favor addition halide anions 15 element. The introduction organic substituents antimony center its oxidation from + III V state provide tunable acidity a breadth applications supramolecular catalysis. performances these antimony-based domain sensing aqueous media illustrate favorable attributes central At same time, recent advances binding catalysis transport across phospholipid membranes speak numerous opportunities lie ahead unique compounds.
Язык: Английский
Процитировано
27
Inorganic Chemistry, Год журнала: 2022, Номер 61(46), С. 18640 - 18652
Опубликована: Ноя. 9, 2022
We report a comprehensive assessment of Lewis acidity for series carbone-stibenium and -bismuthenium ions using the Gutmann-Beckett (GB) method. These new antimony bismuth cations have been synthesized by halide abstractions from (CDC)PnBr3 [(pyCDC)PnBr2][Br] (CDC = carbodicarbene; Pn Sb or Bi; py pyridyl). The reaction (CDC)SbBr3 (1) with one two equivalents AgNTf2 (NTf2 bis(trifluoromethanesulfonyl)imide) AgSbF6 gives stibaalkene mono- dications form [(CDC)SbBr3-n][A]n (2-4; n 1,2; A NTf2 SbF6). trication [(CDC)2Sb][NTf2]3 (5) was also isolated collectively these molecules fill gap among cationic pnictaalkenes. are compared to related CDC-bismaalkene complexes 6-9. With goal preparing highly acidic compounds, tridentate bis(pyridine)carbodicarbene (pyCDC) used as ligand access (10, 12) trications [(pyCDC)Pn][NTf2]3 (Pn (11), Bi (13)), forgoing need second CDC in synthesis 5. bonding situation is elucidated through electron density energy decomposition analyses combination natural orbital chemical valence theory. In each complex, there exists CDC-Pn double interaction, consisting strong σ-bond weaker π-bond, whereby π-bond gradually strengthens increase charge complex. Notably, [(CDC)SbBr][NTf2]2 (4) has an acceptor number (AN) (84) that comparable quintessential acids such BF3, tricationic pnictaalkene 11 13 exhibit ANs 109 Sb) 84 Bi), respectively, which highest values reported any cation. Moreover, calculated fluoride ion affinities (FIAs) 99.8 94.3 kcal/mol, larger than SbF5 (85.1 kcal/mol), suggest superacids.
Язык: Английский
Процитировано
36
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(46)
Опубликована: Сен. 29, 2023
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 chalcogenides Me Y (Y=O, S, Se, Te), nitrogen heterocycles (pyridine, pyrimidine). Insights into adduct formation behavior well situation such E⋅⋅⋅Sb−C moieties were obtained in solution means NMR spectroscopy, solid state X‐ray diffraction, elemental analyses, computational methods (DFT, QTAIM, IQA), respectively.
Язык: Английский
Процитировано
22
Inorganic Chemistry, Год журнала: 2023, Номер 62(11), С. 4590 - 4597
Опубликована: Март 3, 2023
Organobismuth compounds have been studied in various fields, including electronic states, pnictogen bonds, and catalysis. Among them, one of the unique states element is hypervalent state. So far, many issues regarding structures bismuth revealed; meanwhile, influence on properties π-conjugated scaffolds still vailed. Here, we synthesized compound, BiAz, by introducing into azobenzene tridentate ligand as a scaffold. The was evaluated from optical measurements quantum chemical calculations. introduction revealed three significant effects: first, shows position-dependent electron-donating electron-accepting effects. Second, BiAz can larger effective Lewis acidity than tin compound derivatives reported our previous research. Finally, coordination dimethyl sulfoxide transformed similar to compounds. data calculations showed that scaffold were able be changed bismuth. To best knowledge, first demonstrate should new methodology for controlling molecules developing sensing materials.
Язык: Английский
Процитировано
21
The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(6), С. 3909 - 3915
Опубликована: Март 1, 2023
A novel method for the iodine-mediated reduction of phosphine oxides (sulfides) to phosphines using phosphonic acid under solvent-free conditions is described. By a combination H3PO3 and I2, both tertiary monophosphine bis-phosphine were reduced this system, readily producing monodentate bidentate phosphines, respectively, in good yields. Notably, chiral (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl dioxide could be also tolerated without racemization. This new approach inexpensive features simple wide substrate scope.
Язык: Английский
Процитировано
13
Inorganic Chemistry, Год журнала: 2023, Номер 62(33), С. 13566 - 13572
Опубликована: Авг. 8, 2023
We report the results of a computational investigation into fluoride binding by series pentavalent pnictogen Lewis acids: pentahalides (PnX5), tetraphenyl pnictogeniums (PnPh4+), and triphenyl tetrachlorocatecholates (PnPh3Cat). Activation strain energy decomposition analyses adducts not only clearly delineate electrostatic orbital contributions to these acid–base interactions but also highlight importance Pauli repulsion molecular flexibility in determining relative acidity among pnictogens.
Язык: Английский
Процитировано
13
Chemical Science, Год журнала: 2024, Номер 15(30), С. 12118 - 12125
Опубликована: Янв. 1, 2024
(F 5 C 2 ) SbCH P( t Bu) reacts in a FLP-like manner with CS , SO PhNCO/S and (MePh P)AuCl. The AuCl adduct show secondary interactions between the Lewis acidic Sb atom electron rich atoms, intra- intermolecular, respectively.
Язык: Английский
Процитировано
4
Advances in inorganic chemistry, Год журнала: 2023, Номер unknown, С. 237 - 260
Опубликована: Янв. 1, 2023
Язык: Английский
Процитировано
9