FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W1966492024> ?p ?o ?g. }

• W1966492024 endingPage "812" @default.
• W1966492024 startingPage "805" @default.
• W1966492024 abstract "The manipulation of the steric nature of ligands is a key design principle in organometallic reactivity. While general intuition assumes steric effects to be repulsive, recent reports counterintuitively suggested that highly crowded hydrocarbon molecules may be stabilized more strongly than their less bulky analogues as a consequence of dispersion interactions. With the objective of investigating the significance of such attractive intramolecular dispersion forces in organometallic catalysis, we herein studied the effect of dispersion on the accessible geometries and reactivities for two trialkylphosphine ligands of different sizes in Pd-catalyzed cross-coupling reactions: i.e., L = PtBu3 and its smaller analogue L = P(iPr)(tBu2). Those methods that account well for dispersion (e.g., ωB97XD, B3LYP-D3) allowed the first location of bisphosphine-ligated transition states for the oxidative addition of Pd0L2 to aromatic C–O bonds, involving the bulky and widely employed ligand L = PtBu3. DFT methods without dispersion gave rise to dissociation of one phosphine ligand in all cases examined. To probe whether dispersion may even be a reactivity-controlling factor, we also examined the favored site selectivity of the reaction of Pd0L2 with 4-chlorophenyl triflate, for which the selectivity has previously been shown to be dependent on the ligation state of the reactive palladium species. Various DFT methods (PBE, B3LYP, M06L) and basis sets and different solvent models (COSMO-RS, CPCM) were assessed. While for Pd(PtBu3)2 dispersion-free and dispersion-containing methods predicted the monophosphine pathway via PdL and reaction at C–Cl to be favored, striking differences were observed for Pd[P(iPr)(tBu2)]2. Dispersion-free DFT predicted C–OTf addition by Pd[P(iPr)(tBu2)]2 to be disfavored by ΔΔG⧧ ≈ 20 kcal/mol, despite being experimentally accessible. In stark contrast, the involvement of dispersion adequately described the selectivity. The attractive dispersion forces of the crowded trialkyl substituents are therefore a key controlling factor in the competition between mono- and bisligated pathways." @default.
• W1966492024 created "2016-06-24" @default.
• W1966492024 creator A5011396644 @default.
• W1966492024 creator A5047300640 @default.
• W1966492024 creator A5061535844 @default.
• W1966492024 date "2014-12-11" @default.
• W1966492024 modified "2023-10-17" @default.
• W1966492024 title "Dispersion Makes the Difference: Bisligated Transition States Found for the Oxidative Addition of Pd(P<i>t</i>Bu₃)₂ to Ar-OSO₂R and Dispersion-Controlled Chemoselectivity in Reactions with Pd[P(<i>i</i>Pr)(<i>t</i>Bu₂)]₂" @default.
• W1966492024 cites W1964566677 @default.
• W1966492024 cites W1971288381 @default.
• W1966492024 cites W1971643970 @default.
• W1966492024 cites W1971803965 @default.
• W1966492024 cites W1976407428 @default.
• W1966492024 cites W1982515268 @default.
• W1966492024 cites W1982665557 @default.
• W1966492024 cites W1992235100 @default.
• W1966492024 cites W1995736202 @default.
• W1966492024 cites W2003286577 @default.
• W1966492024 cites W2006787866 @default.
• W1966492024 cites W2008041424 @default.
• W1966492024 cites W2009109836 @default.
• W1966492024 cites W2009189836 @default.
• W1966492024 cites W2012522591 @default.
• W1966492024 cites W2012569297 @default.
• W1966492024 cites W2013760130 @default.
• W1966492024 cites W2014298712 @default.
• W1966492024 cites W2021231925 @default.
• W1966492024 cites W2022251773 @default.
• W1966492024 cites W2022674727 @default.
• W1966492024 cites W2028998904 @default.
• W1966492024 cites W2029272084 @default.
• W1966492024 cites W2030699693 @default.
• W1966492024 cites W2037570317 @default.
• W1966492024 cites W2042168436 @default.
• W1966492024 cites W2043656049 @default.
• W1966492024 cites W2046283691 @default.
• W1966492024 cites W2047721585 @default.
• W1966492024 cites W2050480585 @default.
• W1966492024 cites W2055975105 @default.
• W1966492024 cites W2057928456 @default.
• W1966492024 cites W2060941883 @default.
• W1966492024 cites W2063168450 @default.
• W1966492024 cites W2063194970 @default.
• W1966492024 cites W2066875030 @default.
• W1966492024 cites W2069394865 @default.
• W1966492024 cites W2073328513 @default.
• W1966492024 cites W2074888123 @default.
• W1966492024 cites W2078850127 @default.
• W1966492024 cites W2082041430 @default.
• W1966492024 cites W2083297157 @default.
• W1966492024 cites W2086376616 @default.
• W1966492024 cites W2086815955 @default.
• W1966492024 cites W2091702998 @default.
• W1966492024 cites W2092157292 @default.
• W1966492024 cites W2095069219 @default.
• W1966492024 cites W2095773009 @default.
• W1966492024 cites W2102277202 @default.
• W1966492024 cites W2103411876 @default.
• W1966492024 cites W2106323995 @default.
• W1966492024 cites W2112771953 @default.
• W1966492024 cites W2112850441 @default.
• W1966492024 cites W2116810732 @default.
• W1966492024 cites W2123386023 @default.
• W1966492024 cites W2126686651 @default.
• W1966492024 cites W2126740907 @default.
• W1966492024 cites W2127755879 @default.
• W1966492024 cites W2132177201 @default.
• W1966492024 cites W2132525235 @default.
• W1966492024 cites W2135404134 @default.
• W1966492024 cites W2135576821 @default.
• W1966492024 cites W2138280054 @default.
• W1966492024 cites W2139078293 @default.
• W1966492024 cites W2140886907 @default.
• W1966492024 cites W2143981217 @default.
• W1966492024 cites W2144600844 @default.
• W1966492024 cites W2145443414 @default.
• W1966492024 cites W2147154356 @default.
• W1966492024 cites W2157080176 @default.
• W1966492024 cites W2160744209 @default.
• W1966492024 cites W2318853138 @default.
• W1966492024 cites W2319800489 @default.
• W1966492024 cites W2320062077 @default.
• W1966492024 cites W2322365966 @default.
• W1966492024 cites W2324434308 @default.
• W1966492024 cites W2327926457 @default.
• W1966492024 cites W2329762854 @default.
• W1966492024 cites W2333719862 @default.
• W1966492024 cites W2334243492 @default.
• W1966492024 cites W2334421573 @default.
• W1966492024 cites W4256127573 @default.
• W1966492024 doi "https://doi.org/10.1021/om501199t" @default.
• W1966492024 hasPublicationYear "2014" @default.
• W1966492024 type Work @default.
• W1966492024 sameAs 1966492024 @default.
• W1966492024 citedByCount "102" @default.
• W1966492024 countsByYear W19664920242015 @default.
• W1966492024 countsByYear W19664920242016 @default.
• W1966492024 countsByYear W19664920242017 @default.

• next