Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F17%3A10360167" target="_blank" >RIV/00216208:11310/17:10360167 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.organomet.7b00181" target="_blank" >http://dx.doi.org/10.1021/acs.organomet.7b00181</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.organomet.7b00181" target="_blank" >10.1021/acs.organomet.7b00181</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

Popis výsledku v původním jazyce

The stereoelectronic influence of phosphine substituents on the coordination and catalytic properties of phosphinoferrocene carbox-amides was studied for the model compounds R2PfcCONHMe (1a-d), where fc = ferrocene-1,1&apos;-diyl and R = i-Pr (a), t-Bu (b), cyclohexyl (Cy; c), Ph (d), using experimental and DFT-computed parameters. The electronic parameters were examined via 1J(Se,P) coupling constants determined for R2P(Se)fcCONHMe (6a-d) and CO stretching frequencies of the Rh(I) complexes trans-[RhCl(CO)(1-kappa P)2] (7a-d); the steric properties of 1a-d were assessed through Tolman&apos;s ligand cone angles (theta) and solid angles (Omega). Generally, a very good agreement between the calculated and experimental values was observed. Whereas the donor ability of the amidophosphines was found to increase from 1d through 1a,c to 1b, the trends in steric demand suggested by the two parameters differed, reflecting the different spatial properties of the phosphine substituents. In situ NMR studies and catalytic tests on the Suzuki-Miyaura cross-coupling of 4-bromoanisole with a bicyclic 4-tolylborate to give 4-methyl-4&apos;-methoxybiphenyl using [Pd(eta(2):eta(2)-cod)(eta(2)-ma)] (cod = cycloocta-1,5-diene, ma = maleic anhydride) as a Pd(0) precursor revealed that different Pd-1 species (precatalysts) were formed from different ligands and participated in the reaction. Specifically, the bulky and electron-rich donor 1b favored the formation of [Pd(1b)(ma)], while the remaining ligands provided the corresponding bis-phosphine complexes [Pd(1)2(ma)]. The best results in terms of catalyst longevity and efficacy were observed for ligands 1a,c.

Název v anglickém jazyce

Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study

Popis výsledku anglicky

The stereoelectronic influence of phosphine substituents on the coordination and catalytic properties of phosphinoferrocene carbox-amides was studied for the model compounds R2PfcCONHMe (1a-d), where fc = ferrocene-1,1&apos;-diyl and R = i-Pr (a), t-Bu (b), cyclohexyl (Cy; c), Ph (d), using experimental and DFT-computed parameters. The electronic parameters were examined via 1J(Se,P) coupling constants determined for R2P(Se)fcCONHMe (6a-d) and CO stretching frequencies of the Rh(I) complexes trans-[RhCl(CO)(1-kappa P)2] (7a-d); the steric properties of 1a-d were assessed through Tolman&apos;s ligand cone angles (theta) and solid angles (Omega). Generally, a very good agreement between the calculated and experimental values was observed. Whereas the donor ability of the amidophosphines was found to increase from 1d through 1a,c to 1b, the trends in steric demand suggested by the two parameters differed, reflecting the different spatial properties of the phosphine substituents. In situ NMR studies and catalytic tests on the Suzuki-Miyaura cross-coupling of 4-bromoanisole with a bicyclic 4-tolylborate to give 4-methyl-4&apos;-methoxybiphenyl using [Pd(eta(2):eta(2)-cod)(eta(2)-ma)] (cod = cycloocta-1,5-diene, ma = maleic anhydride) as a Pd(0) precursor revealed that different Pd-1 species (precatalysts) were formed from different ligands and participated in the reaction. Specifically, the bulky and electron-rich donor 1b favored the formation of [Pd(1b)(ma)], while the remaining ligands provided the corresponding bis-phosphine complexes [Pd(1)2(ma)]. The best results in terms of catalyst longevity and efficacy were observed for ligands 1a,c.

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/7F14392" target="_blank" >7F14392: Phosphine Ligands for Environmentally Friendly C-C Bond Forming Reactions</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2017

Kód důvěrnosti údajů

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

Název periodika

Organometallics

ISSN

0276-7333

e-ISSN

—

Svazek periodika

36

Číslo periodika v rámci svazku

9

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

14

Strana od-do

1828-1841

Kód UT WoS článku

000401044300022

EID výsledku v databázi Scopus

2-s2.0-85019047731