Selective Ethylene Dimerization by Palladium(II) Complexes Bearing a 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%3A10394009" target="_blank" >RIV/00216208:11310/19:10394009 - isvavai.cz</a>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Selective Ethylene Dimerization by Palladium(II) Complexes Bearing a Phosphinoferrocene Sulfonate Ligand
Original language description
Palladium(II) complexes featuring the hybrid anionic ligand 1'-(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'(4)] (Ar' = 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.
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
7
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
1534-1543
UT code for WoS article
000464248900016
EID of the result in the Scopus database
2-s2.0-85062874016