Non-conventional Behavior of a 2,1-Benzazaphosphole: Heterodiene or Hidden Phosphinidene?

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F21%3A39918130" target="_blank" >RIV/00216275:25310/21:39918130 - isvavai.cz</a>

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202101686" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202101686</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.202101686" target="_blank" >10.1002/chem.202101686</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Non-conventional Behavior of a 2,1-Benzazaphosphole: Heterodiene or Hidden Phosphinidene?

Popis výsledku v původním jazyce

The titled 2,1-benzazaphosphole (1) (i. e. ArP, where Ar=2-(DippN=CH)C6H4, Dipp=2,6-iPr(2)C(6)H(3)) showed a spectacular reactivity behaving both as a reactive heterodiene in hetero-Diels-Alder (DA) reactions or as a hidden phosphinidene in the coordination toward selected transition metals (TMs). Thus, 1 reacts with electron-deficient alkynes RC equivalent to CR (R=CO2Me, C5F4N) giving 1-phospha-1,4-dihydro-iminonaphthalenes 2 and 3, that undergo hydrogen migration producing 1-phosphanaphthalenes 4 and 5. Compound 1 is also able to activate the C=C double bond in selected N-alkyl/aryl-maleimides RN(C(O)CH)(2) (R=Me, tBu, Ph) resulting in the addition products 7-9 with bridged bicyclic [2.2.1] structures. The binding of the maleimides to 1 is semi-reversible upon heating. By contrast, when 1 was treated with selected TM complexes, it serves as a 4e donor bridging two TMs thus producing complexes [mu-ArP(AuCl)(2)] (10), [(mu-ArP)(4)Ag-4][X](4) (X=BF4 (11), OTf (12)) and [mu-ArP(Co-2(CO)(6))] (13). The structure and electron distribution of the starting material 1 as well as of other compounds were also studied from the theoretical point of view.

Název v anglickém jazyce

Non-conventional Behavior of a 2,1-Benzazaphosphole: Heterodiene or Hidden Phosphinidene?

Popis výsledku anglicky

The titled 2,1-benzazaphosphole (1) (i. e. ArP, where Ar=2-(DippN=CH)C6H4, Dipp=2,6-iPr(2)C(6)H(3)) showed a spectacular reactivity behaving both as a reactive heterodiene in hetero-Diels-Alder (DA) reactions or as a hidden phosphinidene in the coordination toward selected transition metals (TMs). Thus, 1 reacts with electron-deficient alkynes RC equivalent to CR (R=CO2Me, C5F4N) giving 1-phospha-1,4-dihydro-iminonaphthalenes 2 and 3, that undergo hydrogen migration producing 1-phosphanaphthalenes 4 and 5. Compound 1 is also able to activate the C=C double bond in selected N-alkyl/aryl-maleimides RN(C(O)CH)(2) (R=Me, tBu, Ph) resulting in the addition products 7-9 with bridged bicyclic [2.2.1] structures. The binding of the maleimides to 1 is semi-reversible upon heating. By contrast, when 1 was treated with selected TM complexes, it serves as a 4e donor bridging two TMs thus producing complexes [mu-ArP(AuCl)(2)] (10), [(mu-ArP)(4)Ag-4][X](4) (X=BF4 (11), OTf (12)) and [mu-ArP(Co-2(CO)(6))] (13). The structure and electron distribution of the starting material 1 as well as of other compounds were also studied from the theoretical point of view.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA18-10222S" target="_blank" >GA18-10222S: Od jednoduchých prekurzorů k unikátním heterocyklům obsahující těžší prvky 15. skupiny</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2021

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

—

Svazek periodika

27

Číslo periodika v rámci svazku

52

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

13

Strana od-do

13149-13160

Kód UT WoS článku

000670513500001

EID výsledku v databázi Scopus

2-s2.0-85109622617