Synthesis and catalytic properties of palladium(ii) complexes with P,π-chelating ferrocene phosphinoallyl ligands and their non-tethered analogues

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F24%3A00585909" target="_blank" >RIV/61388980:_____/24:00585909 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/24:10480929

Výsledek na webu

<a href="https://hdl.handle.net/11104/0353760" target="_blank" >https://hdl.handle.net/11104/0353760</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4dt00961d" target="_blank" >10.1039/d4dt00961d</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis and catalytic properties of palladium(ii) complexes with P,π-chelating ferrocene phosphinoallyl ligands and their non-tethered analogues

Popis výsledku v původním jazyce

Hybrid phosphines usually combine a phosphine moiety with another heteroatom secondary donor group in their structures while compounds equipped with hydrocarbyl pi-donor moieties remain uncommon. This contribution reports the synthesis and structural characterization of the first P/pi-allyl-chelating complexes that were obtained using the structurally flexible and redox-active ferrocene unit as the scaffold, viz. [PdCl(R(2)PfcCHCHCH(2)-eta(3):kappa P)] (1 (R), R = Ph and cyclohexyl (Cy), fc = ferrocene-1,1 '-diyl). These compounds were synthesized from the respective phosphinoferrocene carboxaldehydes R(2)PfcCHO via reaction with vinylmagnesium bromide to generate 1-(phosphinoferrocenyl)allyl alcohols, which were subsequently acetylated. The resulting allyl acetates reacted smoothly with [Pd-2(dba)(3)]/[Et3NH]Cl (dba = dibenzylideneacetone) to produce the target compounds. Complexes 1 (R) and their nontethered analogues [PdCl(eta(3)-C3H5)(FcPR(2)-kappa P)] (5 (R), Fc = ferrocenyl) were evaluated as pre-catalysts for the Pd-catalysed allylic amination of cinnamyl acetate with aliphatic amines and Suzuki-Miyaura-type cross-coupling of 4-tolylboronic acid with benzoyl chloride. In these reactions, better results were achieved with compounds 5 (R) (particularly with 5(Ph)), presumably because they form more stable LPd(0)-type catalysts.

Název v anglickém jazyce

Synthesis and catalytic properties of palladium(ii) complexes with P,π-chelating ferrocene phosphinoallyl ligands and their non-tethered analogues

Popis výsledku anglicky

Hybrid phosphines usually combine a phosphine moiety with another heteroatom secondary donor group in their structures while compounds equipped with hydrocarbyl pi-donor moieties remain uncommon. This contribution reports the synthesis and structural characterization of the first P/pi-allyl-chelating complexes that were obtained using the structurally flexible and redox-active ferrocene unit as the scaffold, viz. [PdCl(R(2)PfcCHCHCH(2)-eta(3):kappa P)] (1 (R), R = Ph and cyclohexyl (Cy), fc = ferrocene-1,1 '-diyl). These compounds were synthesized from the respective phosphinoferrocene carboxaldehydes R(2)PfcCHO via reaction with vinylmagnesium bromide to generate 1-(phosphinoferrocenyl)allyl alcohols, which were subsequently acetylated. The resulting allyl acetates reacted smoothly with [Pd-2(dba)(3)]/[Et3NH]Cl (dba = dibenzylideneacetone) to produce the target compounds. Complexes 1 (R) and their nontethered analogues [PdCl(eta(3)-C3H5)(FcPR(2)-kappa P)] (5 (R), Fc = ferrocenyl) were evaluated as pre-catalysts for the Pd-catalysed allylic amination of cinnamyl acetate with aliphatic amines and Suzuki-Miyaura-type cross-coupling of 4-tolylboronic acid with benzoyl chloride. In these reactions, better results were achieved with compounds 5 (R) (particularly with 5(Ph)), presumably because they form more stable LPd(0)-type catalysts.

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/GA23-06718S" target="_blank" >GA23-06718S: Rigidní a funkční ferrocenové fosfiny</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

53

Číslo periodika v rámci svazku

20

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

8722-8731

Kód UT WoS článku

001214915000001

EID výsledku v databázi Scopus

2-s2.0-85192481570