Tuning Reactivity of Zr-Substituted Keggin Phosphotungstate in Alkene Epoxidation through Balancing H2O2 Activation Pathways: Unusual Effect of Base.

The Zr-monosubstituted Keggin-type dimeric phosphotungstate (Bu4N)8[{PW11O39Zr(µ-OH)(H2O)}2] (1) efficiently catalyzes epoxidation of C═C bonds in various kinds of alkenes, including terminal ones, with aqueous H2O2 as oxidant. Less sterically hindered double bonds are preferably epoxidized despite their lower nucleophilicity. Basic additives (Bu4NOH) in the amount of 1 equiv per dimer 1 suppress H2O2 unproductive decomposition, increase substrate conversion, improve yield of heterolytic oxidation products and oxidant utilization efficiency, and also affect regioselectivity of epoxidation, enhancing oxygen transfer to sterically hindered electron-rich C═C bonds. Acid additives produce a reverse effect on the substrate conversion and H2O2 efficiency. The reaction mechanism was explored using a range of test substrates, kinetic, and spectroscopic tools. The opposite effects of acid and base additives on alkene epoxidation and H2O2 degradation have been rationalized in terms of their impact on hydrolysis of 1 to form monomeric species, [PW11O39Zr(OH)(H2O)x]4- (1-M, x = 1 or 2), which favors H2O2 homolytic decomposition. The interaction of 1 with H2O2 has been investigated by HR-ESI-MS, ATR-FT-IR, and 31P NMR spectroscopic techniques. The combination of spectroscopic studies and kinetic modeling implicated the existence of two types of dimeric peroxo complexes, [Zr2(µ-η2:η2-O2){PW11O39}2(H2O)x]]8- and [{Zr(µ-η2-O2)}2(PW11O39)2(H2O)y]10-, along with monomeric Zr (hydro)peroxo species that begin to dominate at a high excess of H2O2. Both dimeric µ-η2-peroxo intermediates are inert toward alkenes under stoichiometric conditions. V-shape Hammett plots obtained for epoxidation of p-substituted styrenes suggested a biphilic nature of the active oxidizing species, which are monomeric Zr-hydroperoxo and peroxo species. Small basic additives increase the electrophilicity of the catalyst and decrease its nucleophilicity. HR-ESI-MS has identified a dimeric, most likely, bridging hydroperoxo species [{PW11O39Zr}2(µ-O)(µ-OOH)]9-, which may account for the improved epoxidation selectivity and regioselectivity toward sterically hindered C═C bonds.

Ethylene polymerization of nickel catalysts with α-diimine ligands: factors controlling the structure of active species and polymer properties.

α-Diimine and related complexes of late transition metals such as palladium and nickel have been attracting continuing interest as single-site catalysts of ethylene homopolymerization to branched polyolefins, having challenging mechanical properties. The state-of-the art catalysts demonstrate promising catalytic activities, and enhanced thermal stabilities, affording polyethylenes with a variable degree of branching and, in addition, are able to incorporate polar co-monomers into polyethylene structures. At the same time, fundamental understanding of the structure-reactivity relationships of such catalysts mostly remains at the phenomenological level, due to the lack of experimental data on the solution structures of intermediates that drive the polymerization process. In this perspective, we discuss recent advances of α-diimine nickel based catalysts of ethylene polymerization, focusing on the relationships between the catalyst structures on the one hand, and their thermal stabilities and properties of the resulting polyethylene, on the other hand. In addition, some intriguing novel mechanistic findings of these catalyst systems are presented.

NMR spectroscopic identification of Ni(ii) species formed upon activation of (α-diimine)NiBr2 polymerization catalysts with MAO and MMAO.

The nature of Ni(ii) species formed upon the activation of the Brookhart's α-diimine polymerization pre-catalyst LNiBr2 with MAO and MMAO (L = 1,4-bis-2,4,6-dimethylphenyl-2,3-dimethyl-1,4-diazabuta-1,3-diene) has been established using 1H and 13C NMR spectroscopy. The heterobinuclear ion pair [LNiII(µ-Me)2AlMe2]+[MeMAO]- is observed at the initial stage of the reaction of LNiBr2 with MAO at -40 °C, whereas the ion pair [LNiII-tBu]+[MeMMAO]- predominates at the initial stage of the reaction of LNiBr2 with MMAO under the same conditions. At higher temperatures, both ion pairs transform into a Ni(i) species displaying an axially anisotropic EPR spectrum (g‖ = 2.21, g⊥ = 2.06, A⊥ = 1.06 mT).