Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Probing the Influence of Phosphine Substituents on the Donor and Catalytic Properties of Phosphinoferrocene Carboxamides: A Combined Experimental and Theoretical Study
Original language description
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'-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'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'-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.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
<a href="/en/project/7F14392" target="_blank" >7F14392: Phosphine Ligands for Environmentally Friendly C-C Bond Forming Reactions</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2017
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Organometallics
ISSN
0276-7333
e-ISSN
—
Volume of the periodical
36
Issue of the periodical within the volume
9
Country of publishing house
US - UNITED STATES
Number of pages
14
Pages from-to
1828-1841
UT code for WoS article
000401044300022
EID of the result in the Scopus database
2-s2.0-85019047731