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Homogeneous olefin polymerization catalysts are activated in situ with a co-catalyst ([PhN(Me)2-H]+[B(C6F5)4]− or [Ph3C]+[B(C6F5)4]−) in bulk polymerization media. These co-catalysts are insoluble in hydrocarbon solvents, requiring excess co-catalyst (>3 eq.). Feeding the activated species as a solution in an aliphatic hydrocarbon solvent may be advantageous over the in situ activation method. In this study, highly pure and soluble ammonium tetrakis(pentafluorophenyl)borates ([Me(C18H37)2N-H]+[B(C6F5)4]− and [(C18H37)2NH2]+[B(C6F5)4]−) containing neither water nor Cl− salt impurities were prepared easily via the acid–base reaction of [PhN(Me)2-H]+[B(C6F5)4]− and the corresponding amine. Using the prepared ammonium salts, the activation reactions of commercial-process-relevant metallocene (rac-[ethylenebis(tetrahydroindenyl)]Zr(Me)2 (1-ZrMe2), [Ph2C(Cp)(3,6-tBu2Flu)]Hf(Me)2 (3-HfMe2), [Ph2C(Cp)(2,7-tBu2Flu)]Hf(Me)2 (4-HfMe2)) and half-metallocene complexes ([(η5-Me4C5)Si(Me)2(κ-NtBu)]Ti(Me)2 (5-TiMe2), [(η5-Me4C5)(C9H9(κ-N))]Ti(Me)2 (6-TiMe2), and [(η5-Me3C7H1S)(C10H11(κ-N))]Ti(Me)2 (7-TiMe2)) were monitored in C6D12 with 1H NMR spectroscopy. Stable [L-M(Me)(NMe(C18H37)2)]+[B(C6F5)4]− species were cleanly generated from 1-ZrMe2, 3-HfMe2, and 4-HfMe2, while the species types generated from 5-TiMe2, 6-TiMe2, and 7-TiMe2 were unstable for subsequent transformation to other species (presumably, [L-Ti(CH2N(C18H37)2)]+[B(C6F5)4]−-type species). [L-TiCl(N(H)(C18H37)2)]+[B(C6F5)4]−-type species were also prepared from 5-TiCl(Me) and 6-TiCl(Me), which were newly prepared in this study. The prepared [L-M(Me)(NMe(C18H37)2)]+[B(C6F5)4]−-, [L-Ti(CH2N(C18H37)2)]+[B(C6F5)4]−-, and [L-TiCl(N(H)(C18H37)2)]+[B(C6F5)4]−-type species, which are soluble and stable in aliphatic hydrocarbon solvents, were highly active in ethylene/1-octene copolymerization performed in aliphatic hydrocarbon solvents.

CrCl3(thf)3 is a common starting material in the synthesis of organometallic and coordination compounds of Cr. Deposited as an irregular solid with no possibility of recrystallization, it is not a purity guaranteed chemical, causing problems in some cases. In this work, we disclose a well-defined form of the THF adduct of CrCl3 ([CrCl2(μ-Cl)(thf)2]2), a crystalline solid, that enables structure determination by X-ray crystallography. The EA data and XRD pattern of the bulk agreed with the revealed structure. Moreover, its preparation procedure is facile: evacuation of CrCl3·6H2O at 100 °C, treatment with 6 equivalents of Me3SiCl in a minimal amount of THF, and crystallization from CH2Cl2. The ethylene tetramerization catalyst [iPrN{P(C6H4-p-Si(nBu)3)2}2CrCl2]+[B(C6F5)4]− prepared using well-defined [CrCl2(μ-Cl)(thf)2]2 as a starting material exhibited a reliably high activity (6600 kg/g-Cr/h; 1-octene selectivity at 40 °C, 75%), while that of the one prepared using the impure CrCl3(thf)3 was inconsistent and relatively low (~3000 kg/g-Cr/h). By using well-defined [CrCl2(μ-Cl)(thf)2]2 as a Cr source, single crystals of [(CH3CN)4CrCl2]+[B(C6F5)4]− and [{Et(Cl)Al(N(iPr)2)2}Cr(μ-Cl)]2 were obtained, allowing structure determination by X-ray crystallography, which had been unsuccessful when the previously known CrCl3(thf)3 was used as the Cr source.