EXPERIMENTAL ŵŝdžƚƵƌĞǁŝƚŚůŽǁĂĐƟǀŝƚLJ͘dŚĞƐĞǀĂůƵĞƐƌĞƐĞŵďůĞƚŚĞ6ͬϴƌĂƟŽĂŶĚĂĐƟǀŝƚLJŽďƚĂŝŶĞĚŝŶĞdžƉĞƌŝŵĞŶƚϮǁŝƚŚƚŚĞƵƐĞŽĨƵŶƐƵďƐƟƚƵƚĞĚ ůŝŐĂŶĚϭ͘ĐĐŽƌĚŝŶŐůLJ͕ĂďƵůŬŝĞƌN-ƐƵďƐƟƚƵĞŶƚǁĂƐŶŽƚƌĞƐƉŽŶƐŝďůĞĨŽƌƚŚĞƉƌŽĚƵĐƚĚŝƐƚƌŝďƵƟŽŶŝŶƚŚĞŽůŝŐŽŵĞƌŝnjĂƟŽŶĞdžƉĞƌŝŵĞŶƚ͘ dŚĞƌĞƐƵůƚƐƐƚƌŽŶŐůLJƐƵŐŐĞƐƚƚŚĂƚŽŶĞƐƚĞƌŝĐĂůůLJĚĞŵĂŶĚŝŶŐƐƵďƐƟƚƵĞŶƚƉĞƌWĐĞŶƚĞƌŝƐƐƵĸĐŝĞŶƚĨŽƌĞdžĐĞůůĞŶƚϭͲ6ƐĞůĞĐƟǀŝƚLJ͘/Ŷ ĨĂĐƚ͕ĞǀĞŶůĚŽĞƐŶŽƚŚĂǀĞƚŽďĞďŽŶĚĞĚƚŽW͕ǁŚŝĐŚǁĂƐƐŚŽǁŶďLJƉĞƌĨŽƌŵŝŶŐƚŚĞĐĂƚĂůLJnjĞĚƚƌŝŵĞƌŝnjĂƟŽŶƌĞĂĐƟŽŶǁŝƚŚϲĂŶĚϰΎ͘ DŽƌĞŽǀĞƌ͕ƚŚĞǀĞƌLJƐŝŵŝůĂƌĂĐƟǀŝƟĞƐŽĨϰ͕ϰΎ͕ĂŶĚϲŝŶĚŝĐĂƚĞĂŶŝŶƐŝƚƵŵĞƚŚLJůĂƟŽŶĂŶĚ͕ƚŚƵƐ͕ƚŚĂƚƚŚĞE͕EͲďŝƐŵĞƚŚLJů;ĂƌLJůͿƉŚŽƐƉŚŝŶŽ ĂŵŝŶĞƐĂƌĞƉĂƌƚŽĨƚŚĞĂĐƟǀĞƐƉĞĐŝĞƐŝŶƚŚĞĐĂƚĂůLJƐŝƐƌĞĂĐƟŽŶ͘^ŽƵƌĐĞ͗,öhneD͕WĞƵůĞĐŬĞE͕DŽŶŽĞĐLJ<͕ĞƚĂů͘;ϮϬϭϳͿ͘ŚĞŵƚĞĐŚ͕͘ ŽŶůŝŶĞƉƌĞǀŝĞǁ͕K/͗ϭϬ͘ϭϬϬϮͬĐĐƚĐ͘ϮϬϭϳϬϬϰϰϴ͘ Mechanistic Studies on Selective Trimerization of Linear Ơ-Olefins over a Supported Titanium Catalyst... >ŝŶĞĂƌɲͲŽůĞĮŶƐ;>KƐͿĂƌĞŬĞLJƉůĂƞŽƌŵŝŶƚĞƌŵĞĚŝĂƚĞƐǁŚŝĐŚĐĂŶďĞĐŽŶǀĞƌƚĞĚǀŝĂƚƌŝŵĞƌŝnjĂƟŽŶƚŽŚŝŐŚĞƌǀĂůƵĞƉƌŽĚƵĐƚƐ͕ƐƵĐŚĂƐ ĚŝĞƐĞůĂŶĚͬŽƌũĞƚĨƵĞů͕ůƵďƌŝĐĂŶƚƐ͕ĂŶĚƉƌĞĐƵƌƐŽƌƐƚŽƐƵƌĨĂĐƚĂŶƚƐĂŶĚĚĞƚĞƌŐĞŶƚƐ͘dŽĚĂƚĞ͕ŽŶůLJƚǁŽƚƌŝŵĞƌŝnjĂƟŽŶĐĂƚĂůLJƐƚƐŚĂǀĞďĞĞŶ ĨŽƵŶĚƚŽďĞƐĞůĞĐƟǀĞůLJĞīĞĐƟǀĞ͗;Z3TAC)CrCl3ͲǁŚĞƌĞ;Z3dсƚƌŝĂůŬLJůƚƌŝĂnjĂĐLJĐůŽŚĞdžĂŶĞͿĂŶĚŵŽĚŝĮĞĚǀĞƌƐŝŽŶƐŽĨƚŚĞƐŽͲĐĂůůĞĚ&ƵũŝƚĂ ĐĂƚĂůLJƐƚ;;&/ͿͲdŝů3͕ǁŚĞƌĞ&/сN-;ϱͲŵĞƚŚLJůͲϯͲ;ϭͲĂĚĂŵĂŶƚLJůͿƐĂůŝĐLJůŝĚĞŶĞͿͲϮ഻Ͳ;Ϯ഼ͲŵĞƚŚŽdžLJƉŚĞŶLJůͿĂŶŝůŝŶĂƚŽ͘KŶĞŽĨƚŚĞƐĞŵŽĚŝĮĐĂƟŽŶƐ ŝƐĂƐŽůƵďůĞ͕ƐƚŽŝĐŚŝŽŵĞƚƌŝĐĂůůLJĂĐƟǀĂƚĞĚĐĂƚĂůLJƐƚŽďƚĂŝŶĞĚĨƌŽŵƚŚĞƌĞĂĐƟŽŶ Scheme 1. Favored and alternate mechanisms for ŽĨ;&/ͿdŝDĞ3ǁŝƚŚϭĞƋƵŝǀ͘ŽĨ;6&5)3͖ƚŚĞŽƚŚĞƌŝƐƚŚĞƐƵƉƉŽƌƚĞĚĐĂƚĂůLJƐƚ formation of major regioisomer. Ɛ;&/Ϳdŝ͕ŐĞŶĞƌĂƚĞĚďLJĂĚĚŝŶŐ;&/Ϳdŝů3ƚŽDKͲƚƌĞĂƚĞĚ^ŝK2. In both cases, >KƐ;ϭͲƉĞŶƚĞŶĞ͕ϭͲŚĞdžĞŶĞ͕ϭͲĚĞĐĞŶĞͿĂƌĞŽůŝŐŽŵĞƌŝnjĞĚǁŝƚŚŚŝŐŚ;хϵϱйͿ ƐĞůĞĐƟǀŝƚLJĨŽƌƚƌŝŵĞƌƐĂŶĚƐƚƌŽŶŐƉƌĞĨĞƌĞŶĐĞ;ΕϴϱйͿĨŽƌĂƐŝŶŐůĞŝƐŽŵĞƌ ƚŚĞƌĞŽĨ͘dŚĞƐƵƉƉŽƌƚĞĚĐĂƚĂůLJƐƚĞdžŚŝďŝƚƐŚŝŐŚĞƌƉƌŽĚƵĐƟǀŝƚLJ;ĂƐŝƚĚŽĞƐĨŽƌ ĞƚŚLJůĞŶĞƚƌŝŵĞƌŝnjĂƟŽŶͿ͕ŐŝǀŝŶŐƚƵƌŶŽǀĞƌŶƵŵďĞƌƐ;dKEͿĂƐŚŝŐŚĂƐϭϬϯоϭϬϰ ,ŽǁĞǀĞƌ͕ƚŚĞůĞǀĞůƐŽĨƉƌŽĚƵĐƟǀŝƚLJĂƌĞƚŽŽůŽǁĨŽƌƉƌĂĐƟĐĂůĂƉƉůŝĐĂƟŽŶ͘ ,ĞƌĞŝŶ͕ƚŚĞĂƵƚŚŽƌƐƐĞĞŬƚŽŝĚĞŶƟĨLJĂŶĚŝŵƉƌŽǀĞƚŚĞĨĂĐƚŽƌƐƌĞƐƉŽŶƐŝďůĞĨŽƌ ĚŝŵŝŶŝƐŚĞĚƉƌŽĚƵĐƟǀŝƚLJ͘ dŚĞĐĂƚĂůLJƟĐƉĞƌĨŽƌŵĂŶĐĞŽĨƚŚĞƐƵƉƉŽƌƚĞĚĐĂƚĂůLJƐƚƐƚƵĚŝĞĚŚĞƌĞ͕Ɛ;&/Ϳdŝ͕ ĂƉƉĞĂƌƐƚŽďĞŵŽƐƚůLJŝŶĚĞƉĞŶĚĞŶƚŽĨĐŚĂŝŶůĞŶŐƚŚ͕ǁŝƚŚ>KƐƌĂŶŐŝŶŐ ĨƌŽŵƉƌŽƉLJůĞŶĞƚŽϭͲĚĞĐĞŶĞŐŝǀŝŶŐĐŽŵƉĂƌĂďůĞĂĐƟǀŝƟĞƐĂŶĚƐĞůĞĐƟǀŝƟĞƐ͕ ŝŶĐůƵĚŝŶŐĂƐƚƌŽŶŐƉƌĞĨĞƌĞŶĐĞĨŽƌĂƐŝŶŐůĞƌĞŐŝŽŝƐŽŵĞƌ͘dŚĞŵŽƐƚůŝŬĞůLJ ƐĞƋƵĞŶĐĞƚŚĂƚǁŽƵůĚĂĐĐŽƵŶƚĨŽƌƚŚĞƌĞŐŝŽƐĞůĞĐƟǀŝƚLJŝƐĨŽƌŵĂƟŽŶŽĨƚŚĞ ƉƌĞƐƵŵĂďůLJůĞƐƐƐƚĞƌŝĐĂůůLJĐƌŽǁĚĞĚɴ͕ɴ഻ͲĚŝƐƵďƐƟƚƵƚĞĚŵĞƚĂůůĂĐLJĐůŽƉĞŶƚĂŶĞ ĨŽůůŽǁĞĚďLJϭ͕ϮͲŝŶƐĞƌƟŽŶŽĨƚŚĞƚŚŝƌĚ>K͕ĂůƚŚŽƵŐŚĂŶĂůƚĞƌŶĂƚĞŵĞĐŚĂŶŝƐŵ ĐĂŶŶŽƚďĞĞdžĐůƵĚĞĚ;^ĐŚĞŵĞϭͿ͘^ƚƵĚŝĞƐŽĨĞƚŚLJůĞŶĞƚƌŝŵĞƌŝnjĂƟŽŶďLJ;&/Ϳ dŝDĞ3ͬ;6&5)3͕ĂƐŽůƵďůĞĂŶĂůŽŐŽĨƐ;&/Ϳdŝ͕ĚĞŵŽŶƐƚƌĂƚĞĚƚŚĂƚŝŶŝƟĂƟŽŶ ;ĐŽŶǀĞƌƐŝŽŶŽĨƉƌĞͲĐĂƚĂůLJƐƚ;&/ͿdŝDĞ2+ƚŽĂŶĂĐƟǀĞĨŽƌŵͿŝƐƐůŽǁƌĞůĂƟǀĞ ƚŽƉƌŽƉĂŐĂƟŽŶ͕ǁŝƚŚĐĂƚĂůLJƐƚĚĞĐŽŵƉŽƐŝƟŽŶƌŽƵŐŚůLJĐŽŵƉĂƌĂďůĞŝŶƌĂƚĞƚŽ ŝŶŝƟĂƟŽŶ͘dŚŝƐǁŽƵůĚƐƵŐŐĞƐƚƚŚĂƚĨŽƌ>KƐĂůůƚŚƌĞĞƉƌŽĐĞƐƐĞƐƉƌŽĐĞĞĚŽŶ ĂƐŝŵŝůĂƌƟŵĞƐĐĂůĞ͕ŵĂŬŝŶŐƌŝŐŽƌŽƵƐŬŝŶĞƟĐĂŶĂůLJƐŝƐǀĞƌLJĐŚĂůůĞŶŐŝŶŐ͘ ,ŽǁĞǀĞƌ͕ƐĞǀĞƌĂůƐĞŵŝͲƋƵĂŶƟƚĂƟǀĞŽďƐĞƌǀĂƟŽŶƐƉŽŝŶƚƚŽƚŚŝƌĚͲŽƌĚĞƌ ĚĞƉĞŶĚĞŶĐĞŽŶƚŚĞĐŽŶĐĞŶƚƌĂƟŽŶŽĨ>KĂƐǁĞůůĂƐƚŚĞǀŝƌƚƵĂůůLJĞƋƵĂů ŝŶŝƟĂůƌĂƚĞƐĂƚϬĂŶĚϮϱΣͲĮŶĚŝŶŐƐǁŚŝĐŚƚŚĞĂƵƚŚŽƌƐƐƵŐŐĞƐƚĐĂŶďĞ ĞdžƉůĂŝŶĞĚďLJƚŚĞŵĞĐŚĂŶŝƐŵƐŚŽǁŶŝŶ^ĐŚĞŵĞϮ͘^ŽƵƌĐĞ͗^ƚĞĞůŵĂŶ<͕ ůƵƚŚŐĞ͕>ĞŚŵĂŶD͕ĞƚĂů͘;ϮϬϭϳͿ͘^ĂƚĂů͕͘ϳ͗ϰϵϮϮоϰϵϮϲ͘ Scheme 2. Proposed mechanism accounting for thirdorder kinetics. ***** A New Synthesis Route for Alternative Catalysts of Noble Metals ZĞƐĞĂƌĐŚĞƌƐĂƚdŽŚŽŬƵhŶŝǀĞƌƐŝƚLJůĞĚďLJ,ŝƌŽƚŽŵŽEŝƐŚŝŚĂƌĂŚĂǀĞĚĞǀĞůŽƉĞĚĂŶĞǁƐLJŶƚŚĞƐŝƐƌŽƵƚĞĨŽƌĂůƚĞƌŶĂƟǀĞĐĂƚĂůLJƐƚƐŽĨ ŶŽďůĞŵĞƚĂůƐĨŽƌǀĞƌƐĂƟůĞĐŚĞŵŝĐĂůƌĞĂĐƟŽŶƐƚŚĂƚĐŽƵůĚŚĞůƉĂĚĚƌĞƐƐĞŶǀŝƌŽŶŵĞŶƚĂůĐŽŶĐĞƌŶƐ͘tŚŝůĞĐŽŶǀĞŶƟŽŶĂůĐĂƌďŽŶĂĐĞŽƵƐ ĐĂƚĂůLJƐƚƐŚĂǀĞĂŵŽƌƉŚŽƵƐĐĂƌďŽŶĂĐĞŽƵƐƐƚƌƵĐƚƵƌĞƐƚŚĂƚĐĂƵƐĞĂĚĞĐůŝŶĞŝŶĐĂƚĂůLJƟĐĂĐƟǀŝƟĞƐ͕ƚŚĞŶĞǁƐLJŶƚŚĞƐŝƐƌŽƵƚĞĞŶĂďůĞƐƚŚĞ ĨŽƌŵĂƟŽŶŽĨĐĂƌďŽŶĂĐĞŽƵƐĐĂƚĂůLJƐƚƐǁŝƚŚĐŽŶƚƌŽůůĞĚĐŚĞŵŝĐĂůƐƚƌƵĐƚƵƌĞƐůŝŬĞŽƌŐĂŶŝĐͲďĂƐĞĚĐĂƚĂůLJƐƚƐ͘dŚŝƐƐLJŶƚŚĞƐŝƐƌŽƵƚĞŝƐĐĂƉĂďůĞ ŽĨĚĞǀĞůŽƉŝŶŐĂůƚĞƌŶĂƟǀĞĐĂƚĂůLJƐƚƐŽĨŶŽďůĞŵĞƚĂůƐĨŽƌŵĂŶLJĞĐŽͲĨƌŝĞŶĚůLJƚĞĐŚŶŽůŽŐŝĞƐƐƵĐŚĂƐĨƵĞůĐĞůůǀĞŚŝĐůĞƐ͕ŚLJĚƌŽŐĞŶŐĞŶĞƌĂƟŽŶ ĨƌŽŵǁĂƚĞƌĂŶĚK2ƌĞĚƵĐƟŽŶ͘^ŽƵƌĐĞ͗dŽŚŽŬƵhŶŝǀĞƌƐŝƚLJ͕ϳͬϮϱͬϮϬϭϳ͘ The Catalyst Review August 2017 17