The reaction of (N∧N)PdMe 2 (N∧N is Ar−NCMe-MeCN−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 )NCMeMeCN(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.

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.

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.

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.

The first example of nickel-catalyzed hydroamination of allenes is reported. The new cationic [(3-iminophosphine)nickel(allyl)] catalysts have been fully characterized and act regioselectively in the catalytic hydroamination of allenes with secondary amines at room temperature.

The catalytic hydrosilylation of alkynes and ketones has been explored utilizing palladium- and nickel(allyl) complexes supported by 3-iminophosphine ligands. Palladium and nickel demonstrated distinctly different reactivity profiles, with palladium proving very effective for the hydrosilylation of electron-deficient alkynes, while nickel excelled with ketones and internal alkynes. Additionally, in many cases, regioselective hydrosilylation was observed.

This study of the electronic characteristics of (3-iminophosphine)allylpalladium triflate complexes has yielded catalysts with moderate to high activity for the hydroamination of monosubstituted allenes utilizing a wide range of amines. Herein, a new series of these catalysts was synthesized by varying the group on the imine moiety in order to explore the effect of the electronics of the ligand's imine on the catalytic activity for intermolecular hydroamination reactions. Four amine substrates were examined in the catalytic hydroamination of cyclohexylallene, and apparent first-order rate constants were obtained by 1 H NMR spectroscopy. Kinetic isotope effect studies were also performed in order to support a new proposed catalytic cycle in the hydroamination of cyclohexylallene with secondary amines using [(3IP)Pd(allyl)]OTf catalysts.