{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,12]],"date-time":"2026-05-12T14:45:29Z","timestamp":1778597129659,"version":"3.51.4"},"reference-count":46,"publisher":"MDPI AG","issue":"9","license":[{"start":{"date-parts":[[2021,5,8]],"date-time":"2021-05-08T00:00:00Z","timestamp":1620432000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["19-73-10122"],"award-info":[{"award-number":["19-73-10122"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>1-Hexene transformations in the catalytic systems L2MCl2\u2013XAlBui2 (L = Cp, M = Ti, Zr, Hf; L = Ind, rac-H4C2[THInd]2, M = Zr; X = H, Bu i) and [Cp2ZrH2]2-ClAlR2 activated by MMAO-12, B(C6F5)3, or (Ph3C)[B(C6F5)4] in chlorinated solvents (CH2Cl2, CHCl3, o-Cl2C6H4, ClCH2CH2Cl) were studied. The systems [Cp2ZrH2]2-MMAO-12, [Cp2ZrH2]2-ClAlBui2-MMAO-12, or Cp2ZrCl2-HAlBui2-MMAO-12 (B(C6F5)3) in CH2Cl2 showed the highest activity and selectivity towards the formation of vinylidene head-to-tail alkene dimers. The use of chloroform as a solvent provides further in situ dimer dimerization to give a tetramer yield of up to 89%. A study of the reaction of [Cp2ZrH2]2 or Cp2ZrCl2 with organoaluminum compounds and MMAO-12 by NMR spectroscopy confirmed the formation of Zr,Zr-hydride clusters as key intermediates of the alkene dimerization. The probable structure of the Zr,Zr-hydride clusters and ways of their generation in the catalytic systems were analyzed using a quantum chemical approach (DFT).<\/jats:p>","DOI":"10.3390\/molecules26092775","type":"journal-article","created":{"date-parts":[[2021,5,10]],"date-time":"2021-05-10T02:54:58Z","timestamp":1620615298000},"page":"2775","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Ti Group Metallocene-Catalyzed Synthesis of 1-Hexene Dimers and Tetramers"],"prefix":"10.3390","volume":"26","author":[{"given":"Pavel V.","family":"Kovyazin","sequence":"first","affiliation":[{"name":"Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, 141, 450075 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Almira Kh.","family":"Bikmeeva","sequence":"additional","affiliation":[{"name":"Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, 141, 450075 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2876-5622","authenticated-orcid":false,"given":"Denis N.","family":"Islamov","sequence":"additional","affiliation":[{"name":"Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, 141, 450075 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Vasiliy M.","family":"Yanybin","sequence":"additional","affiliation":[{"name":"Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, 141, 450075 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tatyana V.","family":"Tyumkina","sequence":"additional","affiliation":[{"name":"Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, 141, 450075 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2816-2178","authenticated-orcid":false,"given":"Lyudmila V.","family":"Parfenova","sequence":"additional","affiliation":[{"name":"Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, Prospekt Oktyabrya, 141, 450075 Ufa, Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,5,8]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Osakada, K. 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