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Formation of Binuclear Zigzag Hexapentaene Titanium Complexes via a Titanacumulene [Ti=C=C=CH 2 ] Intermediate
Author(s) -
Oswald Tim,
Gelert Tina,
Lasar Christian,
Schmidtmann Marc,
Klüner Thorsten,
Beckhaus Rüdiger
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201706674
Subject(s) - zigzag , crystallography , titanium , synthon , chemistry , stereochemistry , x ray crystallography , crystal structure , diffraction , organic chemistry , physics , geometry , mathematics , optics
Abstract The reaction of bis(η 5 :η 1 ‐pentafulvene)titanium complexes with an allylidenephosphorylide Ph 3 P=C(H)‐ C(H)=CH 2 leads to binuclear zigzag hexapentaene titanium complexes ( Ti2a , Ti2b ). The formation of the central C 6 H 4 unit can be described as a spontaneous double C−H bond activation process, leading to an R 3 P=C=C=CH 2 intermediate, as a synthon for a titanabutatriene fragment [(Cp R ) 2 Ti=C=C=CH 2 ] (R: 2‐adamantyl, CH(p‐tol) 2 ). In a subsequent dimerization Ti2a and Ti2b are formed, proofed by single‐crystal X‐ray diffraction and NMR measurements. The reaction sequence is confirmed by DFT calculations.