Enhanced Reactivity of N-heterocyclic Halophosphines and Phosphenium Cations: The Activation of Carbon―Heteroatom and Boron―Heteroatom Bonds

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00638255" target="_blank" >RIV/61388963:_____/25:00638255 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216275:25310/25:39923457

Výsledek na webu

<a href="https://doi.org/10.1002/chem.202500524" target="_blank" >https://doi.org/10.1002/chem.202500524</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.202500524" target="_blank" >10.1002/chem.202500524</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Enhanced Reactivity of N-heterocyclic Halophosphines and Phosphenium Cations: The Activation of Carbon―Heteroatom and Boron―Heteroatom Bonds

Popis výsledku v původním jazyce

N-heterocyclic phosphines (NHPs), and especially their ionic derivatives, phosphenium cations, have gained significant attention not only as isoelectronic species to N-heterocyclic carbenes (NHCs) but mainly, as highly Lewis acidic, active organocatalysts. A novel type of saturated NHPs has been introduced, with the nitrogen atoms substituted by phosphoramidothioates-{[kappa 2-O,O-(OCH2C(Me)2CH2O)P(= S)]2-mu-[NCH2CH2N]}PX, where X = F, Cl, Br, I, H, Ph, and their derivatives. Thanks to an increased positive charge at the P(III) atom, these compounds are prone to activate C & horbar.O, B & horbar.H, B & horbar.C, or B & horbar.F bonds and open cyclic ethers through the formation of intermediate species-phosphenium cations. The hydrido derivative can effectively catalyze the transfer hydrogenation of azobenzene by ammonia borane when irradiated by UV light at room temperature. The self-ionization of the iodido derivative promoted by the coordination of less sterically demanding N-heterocyclic carbene enables the isolation of a phosphenium cation.

Název v anglickém jazyce

Enhanced Reactivity of N-heterocyclic Halophosphines and Phosphenium Cations: The Activation of Carbon―Heteroatom and Boron―Heteroatom Bonds

Popis výsledku anglicky

N-heterocyclic phosphines (NHPs), and especially their ionic derivatives, phosphenium cations, have gained significant attention not only as isoelectronic species to N-heterocyclic carbenes (NHCs) but mainly, as highly Lewis acidic, active organocatalysts. A novel type of saturated NHPs has been introduced, with the nitrogen atoms substituted by phosphoramidothioates-{[kappa 2-O,O-(OCH2C(Me)2CH2O)P(= S)]2-mu-[NCH2CH2N]}PX, where X = F, Cl, Br, I, H, Ph, and their derivatives. Thanks to an increased positive charge at the P(III) atom, these compounds are prone to activate C & horbar.O, B & horbar.H, B & horbar.C, or B & horbar.F bonds and open cyclic ethers through the formation of intermediate species-phosphenium cations. The hydrido derivative can effectively catalyze the transfer hydrogenation of azobenzene by ammonia borane when irradiated by UV light at room temperature. The self-ionization of the iodido derivative promoted by the coordination of less sterically demanding N-heterocyclic carbene enables the isolation of a phosphenium cation.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA25-17434S" target="_blank" >GA25-17434S: Nesymetrické multitopické ligandy pro kooperativitu kov-kov a kov-ligand</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Svazek periodika

31

Číslo periodika v rámci svazku

46

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

8

Strana od-do

e00524

Kód UT WoS článku

001540299100001

EID výsledku v databázi Scopus

2-s2.0-105012146898