%0 Journal Article %T Conformationally dynamic titanium and zirconium cationic complexes of bis(naphthoxy)pyridine ligands: structure, "oscillation" and olefin polymerization catalysis %+ Institut des Sciences Chimiques de Rennes (ISCR) %+ Total Petrochemicals Research Feluy %A Annunziata, Liana %A Roisnel, Thierry %A Razavi, Abbas %A Carpentier, Jean-François %A Kirillov, Evgueni %< avec comité de lecture %@ 1477-9226 %J Dalton Transactions %I Royal Society of Chemistry %V 46 %N 10 %P 3150-3159 %8 2017-03-07 %D 2017 %R 10.1039/c6dt04680k %M 28134373 %Z Chemical Sciences/Catalysis %Z Chemical Sciences/PolymersJournal articles %X Discrete ionic complexes {ONO}M(CHPh)((η-Ph)CHB(CF)) (M = Ti, 2-Ti; Zr, 2-Zr) have been prepared from the parent neutral dibenzyl precursors and B(CF). Also, a neutral dichloro complex {ONO}ZrCl(MeNH) (3) was synthesized by the reaction of a proligand {ONO}H (1-H2) with (MeN)ZrCl(DME). The compounds were characterized by NMR spectroscopy and X-ray crystallography (for 2-Zr and 3). In the solid state, both 2-Zr and 3 feature meso-like binding of the ligand. VT NMR studies of 2-Ti and 2-Zr revealed that the former species dissociates in solution to form an outer-sphere ion pair (OSIP) that features a complicated dynamic behavior, while the latter compound retains an inner-sphere ion pair (ISIP) structure that interconverts between C-symmetric (meso-like) and C-symmetric (rac-like) conformations. The mechanism of this interconversion was assessed by DFT calculations and the corresponding barrier for the straightforward interconversion was calculated (). %G English %2 https://univ-rennes.hal.science/hal-01501258/document %2 https://univ-rennes.hal.science/hal-01501258/file/Conformationally%20Dynamic%20Titanium%20and%20Zirconium%20Cationic%20Complexes_revised.pdf %L hal-01501258 %U https://univ-rennes.hal.science/hal-01501258 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ SCR-CD %~ SCR_OMC2012 %~ ISCR-OMC %~ STATS-UR1 %~ UR1-SPM %~ ISCR-PRATS %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ UR1-SDLM %~ TEST-UNIV-RENNES %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ TEST-HALCNRS %~ UR1-MMS %~ TEST2-HALCNRS