Effects of Hypervalent Bismuth on Electronic Properties of the Azobenzene Tridentate Ligand and Roles of Lewis Acidity in Controlling Optical Properties

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

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Planar bismuth triamides: a tunable platform for main group Lewis acidity and polymerization catalysis

Chemical Science, Год журнала: 2023, Номер 14(17), С. 4549 - 4563

Опубликована: Янв. 1, 2023

Geometric deformation in main group compounds can be used to elicit unique properties including strong Lewis acidity. Here we report on a family of planar bismuth(iii) complexes (cf. typically pyramidal structure for such compounds), which show geometric acidity that further tuned by varying the steric and electronic features triamide ligand employed. The structural dynamism bismuth was probed both solid solution phase, revealing at least three distinct modes intermolecular association. A modified Gutmann-Beckett method assess their electrophilicity employing trimethylphosphine sulfide addition triethylphosphine oxide as probes, providing insights into preference binding hard or soft substrates. Experimental studies were complemented computational assessment affinities dissection latter intrinsic bond strength energy components. results comparable triarylboranes, with added ability bind two bases simultaneously, reduced discrimination against We also study catalytic efficacy these ring opening polymerization cyclic esters ε-caprolactone rac-lactide. polymers obtained excellent dispersity values high molecular weights low catalyst loadings used. retain performance under industrially relevant conditions, suggesting they may useful less toxic alternatives tin catalysts production medical grade materials. Collectively, establish not only novel neutral platform acidity, but potentially valuable one catalysis.

Язык: Английский

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Combining geometric constraint and redox non-innocence within an ambiphilic PBiP pincer ligand

Chemical Science, Год журнала: 2024, Номер 15(16), С. 6036 - 6043

Опубликована: Янв. 1, 2024

The first pincer ligand featuring a strictly T-shaped pnictogen donor moiety was synthesised. PBiP ligand's redox activity facilitates unprecedented ambiphilic bonding of the Bi centre with transition metals through Bi(6p) orbital.

Язык: Английский

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Hydrogen splitting at a single phosphorus centre and its use for hydrogenation

Nature Chemistry, Год журнала: 2024, Номер 16(8), С. 1261 - 1266

Опубликована: Июнь 27, 2024

Язык: Английский

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Free reactive oxygen species-independent dual enzymatic activity of iron single-atom catalyst for hydrogel-assisted portable visual analysis

Journal of Colloid and Interface Science, Год журнала: 2025, Номер 686, С. 420 - 429

Опубликована: Янв. 31, 2025

Язык: Английский

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Planar Tetracoordinated Silicon (ptSi): Room-Temperature Stable Compounds Containing Anti-van’t Hoff/Le Bel Silicon

Journal of the American Chemical Society, Год журнала: 2020, Номер 143(1), С. 420 - 432

Опубликована: Дек. 21, 2020

While a variety of compounds containing planar tetracoordinated carbon (ptC), the so-called anti-van't Hoff/Le Bel carbon, are known experimentally, stable systems silicon (ptSi) barely known. As part our studies on application stereoelectronically well-defined transition-metal fragments to stabilize in unprecedented bonding modes, we report herein synthesis and full characterization series thermally complexes general formula [Tp′(CO)2MSiC(R1)C(R2)M(CO)2Tp′] (M = Mo, W; R1 R2 Me or H, SiMe3, Ph; Tp′ κ3-N,N′,N″-hydridotris(3,5-dimethylpyrazolyl)borate), which incorporate ptSi atom addition two ptC atoms. The were obtained by reacting metallasilylidyne [Tp′(CO)2M≡Si–M(CO)2(PMe3)Tp′] with alkynes R1C≡CR2 comprehensively analyzed experimental quantum chemical calculations. analyses revealed that is embedded tricyclic trapezoidal core featuring one internal SiC2 outer M–Si–C three-membered rings, fused via Si–C bonds. structural peculiarities evoked presence an center, such as short M–Si bonds, nearly linear M–Si–M spine, long M–C atoms elucidated detailed analysis electronic structure, suggesting factor for stabilization geometry aromaticity central ring having delocalized π electrons. Remarkably, results further indicate existence both centers next each other isolated complexes.

Язык: Английский

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Thermoneutral N−H Bond Activation of Ammonia by a Geometrically Constrained Phosphine

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(44), С. 23625 - 23629

Опубликована: Сен. 3, 2021

A geometrically constrained phosphine bearing a tridentate NNS pincer ligand is reported. The effect of the geometric constraint on electronic structure was probed by theoretical calculations and derivatization reactions. Reactions with N-H bonds result in formation cooperative addition products. thermochemistry these transformations strongly dependent substrate, ammonia activation being thermoneutral. This represents first example molecular compound that reversibly activates via bond scission solution upon mild heating.

Язык: Английский

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Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents**

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(32)

Опубликована: Май 20, 2022

N-containing molecules are mostly derived from ammonia (NH

Язык: Английский

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LNL-Carbazole Pincer Ligand: More than the Sum of Its Parts

Chemical Reviews, Год журнала: 2023, Номер 123(13), С. 8781 - 8858

Опубликована: Июнь 23, 2023

The utility of carbazole in photo-, electro-, and medicinal applications has ensured its widespread use also as the backbone tridentate pincer ligands. In this review, aim is to identify illustrate key features LNL-carbazolide binding transition metal centers (with L = flanking donor moieties, e.g., C, N, P, O-groups) a systematic bottom-up progression marked benefits attainable from (i) rigid aromatic scaffold (modulable both 1,8- 3,6-positions), (ii) significant electronic effect central carbazole-amido metal, tunable sterics electronics (iii) L-moieties (iv) wingtip R-groups on L-donors, with their corresponding influence coordination geometry, d-electron configuration, resultant reactivity. Systematic implementation ligand design strategies not isolation, but combinatorial approach, showcased demonstrate potential for functional molecules that are only modulable adaptable wide-ranging (e.g., stereoselective (photo)catalysis, challenging small molecule activation, SET redox applications, even chemotherapeutics) an indication future research efforts anticipated stem versatile assembly, metals s-, p-, f-block elements.

Язык: Английский

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Reactivity of a Strictly T‐Shaped Phosphine Ligated by an Acridane Derived NNN Pincer Ligand

Chemistry - A European Journal, Год журнала: 2023, Номер 29(39)

Опубликована: Апрель 12, 2023

Abstract The steric tuning of a tridentate acridane‐derived NNN pincer ligand allows for the isolation strictly T‐shaped phosphine that exhibits ambiphilic reactivity. Well‐defined phosphorus‐centered reactivity towards nucleophiles and electrophiles is reported, contrasting with prior reports on this class compounds. Reactions oxidants are also described. latter result in two‐electron oxidation phosphorus atom from +III to +V accompanied by strong geometric distortion ligand. By contrast, cooperative activation E−H (HCl, HBcat, HOMe) bonds proceeds retention redox state. When using H 2 O as substrate, reaction results full disassembly its constituent atoms, highlighting potential platform small molecule reactions.

Язык: Английский

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