The reaction of (N∧N)PdMe 2 (N∧N is Ar−NCMe-MeCN−Ar; Ar = 2,6-bis(diphenylmethyl)-4-methylbenzene) and sulfated zirconia (SZO) in diethyl ether forms organometallic Pd-sites that polymerize ethylene and copolymerize ethylene and methyl acrylate. The Pd-sites bind CO and were studied by infrared and solid-state NMR spectroscopies. Analysis of the reaction mixture shows that more methane than expected evolves during the grafting reaction, suggesting that some Pdsites do not contain a Pd-Me group. Consistent with this observation, deuterium labeling experiments show that ∼9% of palladium sites are active in polymerization reactions. (N∧N)PdMe 2 /SZO polymerizes ethylene with activity as high as 1342 kg PE /(mol active Pd *h) and incorporated up to 0.46% methyl acrylate in copolymerization reactions.
The reaction of (α-diimine)NiMe 2 (α-diimine = (2,6-i Pr 2 -C 6 H 3 )NCMeMeCN(2,6-i Pr 2 -C 6 H 3 )) with partially dehydroxylated sulfated zirconia (SZO 300 ) in MeCN results in the formation of [(αdiimine)NiMe(NCMe)][SZO 300 ] ([1][SZO 300 ]) and methane. Reactions in Et 2 O resulted in mixtures of [(α-diimine)NiMe(OEt 2 )][SZO 300 ] ([2][SZO 300 ]) and [(α-diimine)NiMe(OEt 2 )][MeSZO 300 ] ([2]-[MeSZO 300 ]), which were characterized by solid-state NMR spectroscopy. Contacting these solids with ethylene and monitoring the reaction by solid-state NMR showed that Ni−Me sites insert ethylene. [1][SZO 300 ] and [2][SZO 300 ]/[2][MeSZO 300 ] are active ethylene polymerization catalysts and show properties similar to those of closely related homogeneous catalysts. [2][SZO 300 ]/[2][MeSZO 300 ] copolymerizes ethylene and methyl 10-undecenoate to form copolymers with up to 0.4% incorporation of the polar monomer.
A [(3IP)Pd(allyl)]OTf complex was shown to function efficiently and regioselectively in allene hydrosilylation with phenyl- and diphenylsilane. The catalyst also proved to be highly active for allene hydrosilylation employing a wide range of silanes, each of which produced a single regioisomer.
Fatty nitriles are widely used as
intermediate molecules in the
pharmaceutical and polymer industries. In addition, hydrogenation
of fatty nitriles produces fatty amines that are common surfactants.
In the conventional fatty nitrile process, triglycerides are first
hydrolyzed and the resulting fatty acids are catalytically reacted
with NH
3
in a liquid-phase reaction. In this study, we
report a simpler one-step fatty nitrile production method that involves
a direct vapor-phase reaction of triglycerides with NH
3
in the presence of heterogeneous solid acid catalysts. The reactions
were performed in a tubular reactor maintained at 400 °C into
which triglycerides were injected through an atomizer to allow rapid
volatilization and reaction; NH
3
was fed as a gas. Several
metal oxide catalysts were tested, and reactions in the presence of
V
2
O
5
resulted in near-theoretical fatty nitrile
yields (84 wt % relative to the feed mass). In general, catalysts
with higher acidity such as V
2
O
5
, Fe
2
O
3
, and ZnO showed higher fatty nitrile yields compared
to low acidity catalysts such as ZrO, Al
2
O
3
,
and CuO. Energy balance calculations indicate that the one-step reaction
described here would require significantly lower energy than the conventional
process primarily because of the elimination of the energy-intense
triglyceride hydrolysis.
Cp*Sc-X, where X is a halide, were synthesized and studied by solid-state Sc NMR to determine how the Sc-X bond affects quadrupolar NMR parameters. The experimental quadrupolar coupling constants (C) show that the fluoride has the largest coupling constant and that the iodide has the smallest coupling constant. DFT analysis of this data indicates that the C of these compounds is related to core scandium and halide orbitals, which is related to polarizability of the halide and the Sc-X distance. Cp*ScX(THF) were also investigated by solid-state Sc NMR spectroscopy, and have much smaller C values than the base-free halides. This is related to the change in structure of the THF adduct and occupation of orbitals of π-symmetry that reduce C.
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