Synthesis, Structural Characterization, and Hydroformylation Activity of Rhodium(I) Complexes with a Polar Phosphinoferrocene Sulfonate Ligand
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F19%3A10393760" target="_blank" >RIV/00216208:11310/19:10393760 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=wtjm_PQpXQ" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=wtjm_PQpXQ</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.organomet.8b00800" target="_blank" >10.1021/acs.organomet.8b00800</a>
Alternative languages
Result language
angličtina
Original language name
Synthesis, Structural Characterization, and Hydroformylation Activity of Rhodium(I) Complexes with a Polar Phosphinoferrocene Sulfonate Ligand
Original language description
1'-(Diphenylphosphino)ferrocene-1-sulfonic acid (HL), isolated from the salt (Et3NH)L on an ion exchanger, reacts with Rh(I) complexes [Rh(acac)(CO)(PR3)] (acac = acetylacetonato-kappa O-2,O') to give complexes of the type [Rh(CO)(PR3)(Ph(2)PfcSO(3)-kappa O-2,P)] (1ad; R = Ph (a), Cy (b), 2-furyl (c), and OMe (d); fc = ferrocene-1,1'-diyl). In an analogous reaction with [Rh(acac)(nbd)] (nbd = eta(2):eta(2)-norbornadiene), HL produces [Rh(nbd)(Ph(2)PfcSO(3)-kappa O-2,P)] (2). Adding (Et3NH)L (2 equiv per Rh) to [Rh(;-Cl)(CO)(2)](2) and [Rh(acac)(CO)(2)] gives rise to the cationic complexes trans-(Et3NH)(2)[RhCl(CO)(Ph(2)PfcSO(3)-kappa P)(2)] (3) and (Et3NH)[Rh(CO)(Ph(2)PfcSO(3)-kappa O-2,P)(Ph(2)PfcSO(3)-kappa P)] (4), respectively. In complex 4, resulting from the simultaneous substitution of a CO ligand and acidbase replacement of the acac ligand, the P-monodentate and O,P-chelating phosphinoferrocene sulfonate ligands rapidly interconvert (in a solution). All compounds were characterized by spectroscopic methods and by elemental analysis, and the crystal structures of 1aMe(2)CO, solvated 1b, 2, and 4H(2)O were determined. Furthermore, the catalytic activity of all Rh(I) complexes was assessed in hydroformylation of vinyl acetate under solvent-free conditions at 80 degrees C and at 20 bar of synthesis gas (H-2/CO = 1:1). High conversion with good selectivity to iso-aldehyde was observed for 1a(1)/2H2O and 4(1)/2H2O. When applied to on-water hydroformylation of 1-hexene (80 degrees C/10 bar), the complexes mainly promoted 1-hexene isomerization to 2-hexene. However, two of them, 1a(1)/2H2O and 1c, exhibited reasonable selectivity to aldehydes and preferentially produced the linear product (n/iso ratios up to 3).
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - 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
Result continuities
Project
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Continuities
S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2019
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
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Volume of the periodical
38
Issue of the periodical within the volume
2
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
479-488
UT code for WoS article
000457206100034
EID of the result in the Scopus database
2-s2.0-85059676247