Synthesis and Catalytic Use of Polar Phosphinoferrocene Amidosulfonates Bearing Bulky Substituents at the Ferrocene Backbone

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F21%3A10430080" target="_blank" >RIV/00216208:11310/21:10430080 - isvavai.cz</a>

Result on the web

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=bzGxcbGi0i" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=bzGxcbGi0i</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.organomet.1c00244" target="_blank" >10.1021/acs.organomet.1c00244</a>

Result language

angličtina

Original language name

Synthesis and Catalytic Use of Polar Phosphinoferrocene Amidosulfonates Bearing Bulky Substituents at the Ferrocene Backbone

Original language description

Anionic phosphinoferrocene amidosulfonates bearing sterically demanding tert-butyl substituents in positions 3 and 3&apos; of the ferrocene scaffold, viz. rac-(Et3NH)[Fe(η(5)-tBuC5H3PR2)-(η(5)-tBuC5H3C(O)NHCH2SO3)] (R = phenyl, cyclohexyl), were synthesized by amidation of the corresponding phosphinocarboxylic acids, [Fe(η(5)-tBuC5H3PR2)(η(5)-tBuC5H3CO2H)]. These ditopic polar phosphinoferrocenes and their non-tert-butylated analogues have been used as ligands to prepare zwitterionic (η(3)-ally) palladium(II) complexes [Pd(η(3)-C3H5){Fe(η(5)-R&apos;C5H3PR2)(η(5)-R&apos;C5H3C(O)NHCH2SO3)}] (R&apos; = H, tBu; R = Ph, Cy). Depending on the isolation procedure and crystallization conditions, some complexes were isolated in two isomeric forms which differed in the coordination of the amidosulfonate pendant group, where either amide or sulfonated oxygen ligated the Pd(II) center. The preference for coordination of the amide or sulfonate oxygen atoms has been explained by the interplay of electrostatic and solvation effects and further supported by DFT calculations. The (η(3)-ally)Pd-II complexes have been applied as defined precatalysts for Pd-catalyzed C-H arylation of an unprotected indole with aryl iodides in polar solvents. Under the optimized reaction conditions at 100 degrees C in water, C2-arylation proceeded selectively with various aryl iodides to produce the respective 2-arylindoles in acceptable yields at a low catalyst loading (1 mol % Pd) and in the absence of any phase transfer agent. The catalyst possessing tert-butyl groups at the ferrocene core and an electron-rich dicyclohexylphosphino group exhibited the best catalytic performance.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10402 - Inorganic and nuclear chemistry

Project

—

Continuities

S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2021

Confidentiality

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

Name of the periodical

Organometallics

ISSN

0276-7333

e-ISSN

—

Volume of the periodical

40

Issue of the periodical within the volume

12

Country of publishing house

US - UNITED STATES

Number of pages

11

Pages from-to

1934-1944

UT code for WoS article

000669544500018

EID of the result in the Scopus database

2-s2.0-85108561399