Synthesis, Structural Characterization, and Hydroformylation Activity of Rhodium(I) Complexes with a Polar Phosphinoferrocene Sulfonate Ligand

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis, Structural Characterization, and Hydroformylation Activity of Rhodium(I) Complexes with a Polar Phosphinoferrocene Sulfonate Ligand

Popis výsledku v původním jazyce

1&apos;-(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&apos;) 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&apos;-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).

Název v anglickém jazyce

Synthesis, Structural Characterization, and Hydroformylation Activity of Rhodium(I) Complexes with a Polar Phosphinoferrocene Sulfonate Ligand

Popis výsledku anglicky

1&apos;-(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&apos;) 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&apos;-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).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

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

Rok uplatnění

2019

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

38

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

479-488

Kód UT WoS článku

000457206100034

EID výsledku v databázi Scopus

2-s2.0-85059676247