The silylium‐like surface species [iPr3Si][(RFO)3Al−OSi≡)] activates (N^N)Pd(CH3)Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH3][(RFO)3Al−OSi≡)] (
- Award ID(s):
- 1800561
- NSF-PAR ID:
- 10147324
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 11
- Issue:
- 6
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 1510 to 1517
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract 1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that1 shows similar reactivity patterns as (N^N)Pd(CH3)Cl activated with Na[B(ArF)4]. Multinuclear13C{27Al} RESPDOR and1H{19F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH3+and [(RFO)3Al−OSi≡)].1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH3]+in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions.1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate. -
Abstract The silylium‐like surface species [iPr3Si][(RFO)3Al−OSi≡)] activates (N^N)Pd(CH3)Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH3][(RFO)3Al−OSi≡)] (
1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that1 shows similar reactivity patterns as (N^N)Pd(CH3)Cl activated with Na[B(ArF)4]. Multinuclear13C{27Al} RESPDOR and1H{19F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH3+and [(RFO)3Al−OSi≡)].1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH3]+in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions.1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate. -
null (Ed.)A series of new Ce( iv ) based fluorides with two different compositions, Cs 2 MCe 3 F 16 (M = Ni 2+ , Co 2+ , Mn 2+ , and Zn 2+ ) and Na 3 MCe 6 F 30 (M = Al 3+ , Ga 3+ , Fe 3+ , and Cr 3+ ) were synthesized as high quality single crystals via a mild hydrothermal route. The compounds with the composition Cs 2 MCe 3 F 16 (M = Ni 2+ , Co 2+ , Mn 2+ , and Zn 2+ ) crystallize in the hexagonal crystal system with space group P 6 3 / mmc and are isotypic with the uranium analogs, whereas the Na 3 MCe 6 F 30 (M = Al 3+ , Ga 3+ , Fe 3+ , and Cr 3+ ) compounds crystallize in the trigonal space group P 3̄ c 1 and are isotypic with the uranium and thorium analogs Na x MM′ 6 F 30 (M′ = Th, U). The Cs 2 MCe 3 F 16 compounds exhibit a complex 3D crystal structure constructed of edge-sharing cerium trimers, in which all three Ce atoms share a common μ 3 -F unit. The Na 3 MCe 6 F 30 compounds are constructed of edge- and vertex-sharing cerium polyhedra connected to each other to form Ce 6 F 30 6− framework, which can accommodate only relatively smaller trivalent cations (M 3+ = Al 3+ , Ga 3+ , Fe 3+ , and Cr 3+ ) as compared to uranium and thorium analogs. Magnetic susceptibility measurements were carried out on the samples of Cs 2 MCe 3 F 16 (M = Ni 2+ and Co 2+ ), which exhibit paramagnetic behavior.more » « less
-
Abstract Al(OC(CF3)3)(PhF) reacts with silanols present on partially dehydroxylated silica to form well‐defined ≡SiOAl(OC(CF3)3)2(O(Si≡)2) (
1 ).27Al NMR and DFT calculations with a small cluster model to approximate the silica surface show that the aluminum in1 adopts a distorted trigonal bipyramidal coordination geometry by coordinating to a nearby siloxane bridge and a fluorine from the alkoxide. Fluoride ion affinity (FIA) calculations follow experimental trends and show that1 is a stronger Lewis acid than B(C6F5)3and Al(OC(CF3)3)(PhF) but is weaker than Al(OC(CF3)3) andiPr3Si+. Cp2Zr(CH3)2reacts with1 to form [Cp2ZrCH3][≡SiOAl(OC(CF3)3)2(CH3)] (3 ) by methide abstraction. This reactivity pattern is similar to reactions of organometallics with the proposed strong Lewis acid sites present on Al2O3. -
Abstract Al(OC(CF3)3)(PhF) reacts with silanols present on partially dehydroxylated silica to form well‐defined ≡SiOAl(OC(CF3)3)2(O(Si≡)2) (
1 ).27Al NMR and DFT calculations with a small cluster model to approximate the silica surface show that the aluminum in1 adopts a distorted trigonal bipyramidal coordination geometry by coordinating to a nearby siloxane bridge and a fluorine from the alkoxide. Fluoride ion affinity (FIA) calculations follow experimental trends and show that1 is a stronger Lewis acid than B(C6F5)3and Al(OC(CF3)3)(PhF) but is weaker than Al(OC(CF3)3) andiPr3Si+. Cp2Zr(CH3)2reacts with1 to form [Cp2ZrCH3][≡SiOAl(OC(CF3)3)2(CH3)] (3 ) by methide abstraction. This reactivity pattern is similar to reactions of organometallics with the proposed strong Lewis acid sites present on Al2O3.