2-Alkylphosphino-1-Boraadamantanes DOI
Kurt F. Hoffmann, Rayni P. Noriega,

Paul D. Boyle

и другие.

Chemical Communications, Год журнала: 2024, Номер 60(69), С. 9222 - 9225

Опубликована: Янв. 1, 2024

Boraadamantanes are a privileged class of caged group 13 compounds having trigonal pyramidal (non-VSEPR) ground-state. The Lewis acid-base chemistry this type compound is underdeveloped when compared to acyclic derivatives. This report provides the first examples bifunctional boraadamantanes with an appended phosphine moiety (also phosphorus-boron bond). Using scaffold, boraadamantane coordination accessed for time.

Язык: Английский

Cooperative Heterobimetallic CO2 Activation Involving a Mononuclear Aluminum(II) Intermediate DOI
Roushan Prakash Singh, Kevin P. Quirion, Joshua Telser

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 3, 2025

Molecular chemistry of aluminum most commonly involves AlIII ions due to their noble gas electronic configurations. In contrast, the AlII is underexplored and may contain undiscovered reaction manifolds. Here, we report CO2 activation a transient intermediate supported by chelating, dianionic ligand investigate structure details mechanisms required access this reactivity. We found that heterobinuclear complex, (NON)Al-FeCp(CO)2 (1), undergoes Al-Fe bond homolysis at ambient conditions reveal [(NON)Al]•/[CpFe(CO)2]• radical pair in situ. The presence predominantly Al-centered spin density (i.e., an ion) within was established quantum-chemical calculations with experiments which scavengers (TEMPO, benzophenone) induce homolysis. Exposure 1 atmosphere resulted insertion into bond. This net 2-electron reduction process computationally modeled using functional theory direct dynamics simulations, revealing two 1-electron steps and, thus, depends on stabilization high-energy [CO2]•- coordination aluminum. mechanism for unexpected given canonical predisposition multielectron processes demonstrates possibility discovering new profiles earth-abundant elements unusual oxidation states.

Язык: Английский

Процитировано

1

Combining geometric constraint and redox non-innocence within an ambiphilic PBiP pincer ligand DOI Creative Commons
Peter Coburger, Ana Guilherme Buzanich, Franziska Emmerling

и другие.

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

Процитировано

8

Molecular-strain induced phosphinidene reactivity of a phosphanorcaradiene DOI Creative Commons
Yizhen Chen, Peifeng Su, Dongmin Wang

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 29, 2024

Abstract Phosphanorcaradienes are an appealing class of phosphorus compounds that can serve as synthons transient phosphinidenes. However, the synthesis such species is a formidable task owing to their intrinsic high reactivity. Herein we report straightforward synthesis, characterization and reactivity studies phosphanorcaradiene, in which one benzene rings flanking fluorenyl substituents intramolecularly dearomatized through attachment atom. It facilely obtained by reduction phosphorus(III) dichloride precursor with potassium graphite. Despite being thermally robust, it acts synthetic equivalent phosphinidene. reacts trimethylphosphine isonitrile yield phosphanylidene-phosphorane 1-phospha-3-azaallene, respectively. When treated two molar equivalents azide, iminophosphane bis(imino)phosphane isolated, Moreover, capable activating ethylene alkyne afford [1 + 2] cycloaddition products, well oxidative cleavage Si–H N–H bonds secondary phosphines. All reactions proceed smoothly at room temperature without presence transition metals. The driving force for these most likely ring-constraint three-membered PC 2 ring recovery aromaticity ring.

Язык: Английский

Процитировано

6

Why Are Some Pnictogen(III) Pincer Complexes Planar and Others Pyramidal? DOI Creative Commons

Tyler J. Hannah,

Tamina Kirsch,

Saurabh S. Chitnis

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(57)

Опубликована: Июль 30, 2024

Geometrically-constrained pnictogen pincer complexes have emerged in recent years as platforms for unique stoichiometric and catalytic chemical transformations. These feature dynamic conformations ranging from fully planar at the centre to distorted-pyramidal geometries, well variation between phases. Although valued reactivity of is ascribed their there no unified model explain observed conformational outcomes across different ligands centres. Here we propose such a through computational analysis more than 1300 structures 64 (16 4 heavy pnictogens), explaining experimental observations making new predictions. By looking signatures bond stability (bond lengths, Wiberg indices) delocalization (NPA charges, Hirshfeld charges), our framework posits pnictogen-based σ-bonding effect that favours pyramidalization exists competition with ligand-based π-bonding planarity. Variations structure function identity, ligand tethering, electronics, aromaticity can be reconciled reference balance these two opposing forces. Careful consideration σ/π-bonding effects may aid rational design future predictable geometries reactivities.

Язык: Английский

Процитировано

4

Diverse Functionality of Molecular Germanium: Emerging Opportunities as Catalysts DOI
Nilanjana Mukherjee, Moumita Majumdar

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(35), С. 24209 - 24232

Опубликована: Авг. 22, 2024

Fundamental research on germanium as the central element in compounds for bond activation chemistry and catalysis has achieved significant feats over last two decades. Designing strategies small molecule activations ultimate catalysts established capitalize orbital modalities of germanium, apparently imitating transition-metal frontier orbitals. There is a growing body examples contemporary implicating tunability orbitals through avant-garde approaches such geometric constrained empowered reactivity, bimetallic complementarity, cooperative etc. The goal this Perspective to provide readers with an overview emerging opportunities field germanium-based by perceiving underlying key principles. This will help convert discrete set findings into more systematic vision catalyst designs. Critical exposition germanium's participations evokes challenges involved innovative designs, wherein viewpoints are provided. We close addressing forward-looking directions catalytic manifold development. hope that be motivational applied constituent pragmatic catalysts.

Язык: Английский

Процитировано

4

Synthesis and redox catalysis of Carbodiphosphorane ligated stannylene DOI Creative Commons
Zhuchunguang Liu, Zhijun Wang, Mu Huan

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 14, 2024

Heavier group 14 carbene analogues, exhibiting transition-metal-like behavior, display remarkable capability for small molecule activation and coordination chemistry. However, their application in redox catalysis remains elusive. In this paper, we report the synthesis isolation of a stannylene with carbodiphosphorane ligand. The nucleophilic reactivity at divalent tin center is elucidated by computational studies. Moreover, exhibits catalytic activity hydrodefluorination reaction fluoroarenes. Mechanistic investigations into elementary steps confirm Sn

Язык: Английский

Процитировано

3

A focus on phosphinophosphination of apolar bonds by a structurally constrained P–P bonded system DOI Creative Commons

Tyler J. Hannah,

Saurabh S. Chitnis

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This article highlights recent work by Greb et al. on the phosphinophosphination of alkenes, alkynes, and carbonyls, with a focus how polarity P–P bond controls scope resulting reactivity.

Язык: Английский

Процитировано

0

Flash Communication: Ligand Centered Cooperative O–H Bond Splitting by a Mo(CO)5(phosphine) Complex DOI Creative Commons

Sotirios Pavlidis,

Josh Abbenseth

Organometallics, Год журнала: 2025, Номер unknown

Опубликована: Янв. 22, 2025

The synthesis and reactivity of a molybdenum carbonyl complex ligated by geometrically constrained phosphorus trisamide are reported. Reaction with potassium tert-butoxide or methanol triggers ligand-centered substrate activation, leading to planarization the phosphine donor ligand. P–O bond formation, decarbonylation, insertion center into ligand P–N result in formation tetracarbonyl complexes rigid N,P-chelate ligands.

Язык: Английский

Процитировано

0

The Outstanding Ambiphilicity of Trialkylstibines among Trialkylpnictines: Power for Stepwise Deoxygenation and N–N Coupling of Nitroarenes DOI
Zichen Zhang, Kunlong Li, Minghao Huang

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

The ongoing discovery of highly reactive ambiphilic main-group species has significantly advanced the development chemistry, particularly in realms small molecule activation and catalysis. Theoretically, compounds featuring smaller HOMO–LUMO gaps gain stronger ambiphilicity higher reactivity. In this work, we fundamentally demonstrate that Me3Sb holds smallest gap among trimethylpnictines, indicating its outstanding ambiphilicity. Correspondingly, superior reactivity toward deoxygenation electron-deficient nitroarenes been unambiguously revealed through control experiments. Furthermore, unprecedented SbIII/SbVO cycling between trialkylstibines their oxides established for catalytic transformation into azoxyarenes/azoarenes. This study opens a new chapter organoantimony derivatives fields redox

Язык: Английский

Процитировано

0

Meta-Xylene-Based Diamines with Protected Benzyl Sites: Potential NCN Pincer Ligands with Tunable Steric Profiles DOI Creative Commons

Tamina Kirsch,

Toren Hynes,

Jason D. Masuda

и другие.

Molecules, Год журнала: 2025, Номер 30(6), С. 1331 - 1331

Опубликована: Март 16, 2025

Bulky NCN aryl-diamides featuring methyl groups in the benzyl positions were synthesized with aim of creating a new class meta-xylene-based trianionic pincer ligands where common decomposition pathway metal complexes via C-H activation is prevented. Sterically demanding substituents on furthermore provide steric protection centre and can help prevent dimerization complexes. While double deprotonation formation dilithium salt was straightforward, difficulties encountered when attempting to deprotonate ipso-CH proton central aryl ring yield ligands. This stands contrast related without benzylic positions. Experimental theoretical investigations led conclusion that challenges third are likely caused by an interplay increased electron density at nitrogen atoms hindrance. Both effects originate introduction positions, which make targeted less accessible. These results further insight into impact both electronic properties ligands, may find utility coordination chemistry applications metalation be achieved direct rather than requiring triple deprotonation.

Язык: Английский

Процитировано

0