Selective Ethylene Dimerization by Palladium(II) Complexes Bearing a Phosphinoferrocene Sulfonate Ligand

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F19%3A10394009" target="_blank" >RIV/00216208:11310/19:10394009 - isvavai.cz</a>

Výsledek na webu

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

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.organomet.9b00015" target="_blank" >10.1021/acs.organomet.9b00015</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Selective Ethylene Dimerization by Palladium(II) Complexes Bearing a Phosphinoferrocene Sulfonate Ligand

Popis výsledku v původním jazyce

Palladium(II) complexes featuring the hybrid anionic ligand 1&apos;-(diphenylphosphino)ferrocene-1-sulfonate (L-), viz., trans-(Et3NH)(2)[Pd-(mu-Cl)Me(L-kappa P)](2) (1), [Pd(Me)(dmap-kappa N-1)(L-kappa O-2,P)](2; dmap = 4-(dimethylamino)pyridine), and [Pd(eta(3)-allyl)(L-kappa O-2,P)] (6), were synthesized and together with the previously reported compounds trans- (Et3NH)(2)[PdCl2(L-kappa P)(2)] and [Pd(L-CY)(L-kappa O-2,P)] (L-CY = 2-[(dimethylamino-kappa N)methyl]phenyl-kappa C-1 and 2-[(methylthio-kappa S)methyl]phenyl-kappa C-1) tested as precatalysts for Pd-catalyzed ethylene dimerization. Only compound 1 gave rise to an active catalyst after activation by sequential halogen removal with Tl[PF6] and Na[BAr&apos;(4)] (Ar&apos; = 3,5-bis(trifluoromethyl)phenyl) in chloroform. Thus, the formed catalyst efficiently mediated the dimerization of ethylene showing both good activity (TOF approximate to 95 h(-1)) and high selectivity for 1-butene (95%) at 21 degrees C and 30 bar of ethylene pressure. DFT calculations have shown that the dimerization reaction is thermodynamically preferred over the formation of higher oligomers and that O,P-chelate coordination of the phosphinosulfonate ligand in all Pd(II) reaction intermediates is vital for the catalytic process. In particular, the O,P-chelating phosphinoferrocene sulfonate ligand stabilizes and electronically differentiates the reaction intermediates and favors concerted ethyl migration to coordinated ethylene giving rise to 1-butene.

Název v anglickém jazyce

Selective Ethylene Dimerization by Palladium(II) Complexes Bearing a Phosphinoferrocene Sulfonate Ligand

Popis výsledku anglicky

Palladium(II) complexes featuring the hybrid anionic ligand 1&apos;-(diphenylphosphino)ferrocene-1-sulfonate (L-), viz., trans-(Et3NH)(2)[Pd-(mu-Cl)Me(L-kappa P)](2) (1), [Pd(Me)(dmap-kappa N-1)(L-kappa O-2,P)](2; dmap = 4-(dimethylamino)pyridine), and [Pd(eta(3)-allyl)(L-kappa O-2,P)] (6), were synthesized and together with the previously reported compounds trans- (Et3NH)(2)[PdCl2(L-kappa P)(2)] and [Pd(L-CY)(L-kappa O-2,P)] (L-CY = 2-[(dimethylamino-kappa N)methyl]phenyl-kappa C-1 and 2-[(methylthio-kappa S)methyl]phenyl-kappa C-1) tested as precatalysts for Pd-catalyzed ethylene dimerization. Only compound 1 gave rise to an active catalyst after activation by sequential halogen removal with Tl[PF6] and Na[BAr&apos;(4)] (Ar&apos; = 3,5-bis(trifluoromethyl)phenyl) in chloroform. Thus, the formed catalyst efficiently mediated the dimerization of ethylene showing both good activity (TOF approximate to 95 h(-1)) and high selectivity for 1-butene (95%) at 21 degrees C and 30 bar of ethylene pressure. DFT calculations have shown that the dimerization reaction is thermodynamically preferred over the formation of higher oligomers and that O,P-chelate coordination of the phosphinosulfonate ligand in all Pd(II) reaction intermediates is vital for the catalytic process. In particular, the O,P-chelating phosphinoferrocene sulfonate ligand stabilizes and electronically differentiates the reaction intermediates and favors concerted ethyl migration to coordinated ethylene giving rise to 1-butene.

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

7

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

1534-1543

Kód UT WoS článku

000464248900016

EID výsledku v databázi Scopus

2-s2.0-85062874016