Additions and corrections

Synthesis, Structure, Coordination Expansion and Theoretical Modelling of Dichlorobis(phenoxo) Titanium(IV) Complexes

“…However, complex 3 is closely related to [TiCl 2 (OC 6 H 3 Me 2 -2,6) 2 ] for which an X-ray crystal structure determination has shown a monomeric tetrahedral structure with Ti-O bond lengths of 1.734(7) and 1.736(8) Å, Ti-Cl bond lengths of 2.192(4) and 2.211(4) Å [9] and an ipso-C resonance in the 13 C NMR spectrum at δ = 167.8 ppm. [8] In the octahedral adduct [TiCl 2 (OC 6 H 3 Me 2 -2,6) 2 (dpeda)] [dpeda = (1S,2S)-diphenylethylenediamine] the Ti-O bond lengths increase to 1.804(4) and 1.787(4) Å, the Ti-Cl bond lengths to 2.353(2) Å and the ipso-C resonance is at δ = 166.0 ppm. [7] The standard deviations for the C-O bond lengths do not allow reliable bond length comparisons to be made for these complexes.…”

“…This indicated that the thermalisation reaction is not successful with this sterically demanding phenol. [8] A sample of [TiCl 2 (OC 6 H 2 {CMe 3 } 2 -2,6-Me-4) 2 ] prepared by the reaction of TiCl 4 and LiOC 6 H 2 (CMe 3 ) 2 -2,6-Me-4 [8] did not react with dmbipy and is reported not to react with pyridine. [8] These results indicate that 2,6-di-tert-butyl substitu-ents represent the steric limit for coordination expansion about the titanium centre.…”

“…[8] A sample of [TiCl 2 (OC 6 H 2 {CMe 3 } 2 -2,6-Me-4) 2 ] prepared by the reaction of TiCl 4 and LiOC 6 H 2 (CMe 3 ) 2 -2,6-Me-4 [8] did not react with dmbipy and is reported not to react with pyridine. [8] These results indicate that 2,6-di-tert-butyl substitu-ents represent the steric limit for coordination expansion about the titanium centre. Several unsymmetrically substituted phenols were also thermalised with TiCl 4 in toluene giving bis(phenoxo) complexes which have not been reported before.…”

“…[7] From the synthetic point of view, complexes containing tert-butyl or phenyl groups in the 2,6-positions of the aryloxo ring have received the most attention. [5,[8][9][10] However, little is known about bis(phenoxo) complexes containing ligands which are less sterically demanding. For example, [TiCl 2 (OC 6 H 5 ) 2 ] has a dimeric structure in the solid state [11] and there is conflicting evidence for the structure in solution, [12,13] [TiCl 2 (OC 6 H 3 Me 2 -2,6) 2 ] has a monomeric solid-state structure, [9] ArNH 2 and tetrahydrofuran) which have been characterised only by analytical data and IR spectroscopy.…”

Synthesis and characterization of bis(indenyl) zirconium aryloxide derivatives and their use in α‐olefin polymerization

“…Information on the effects of s-ligands other than methyl or chloride are, so far, quite limited, even if an increasing interest toward complexes bearing metal alkoxide bonds has been reported. [10][11][12][13][14][15] The chemistry of metal aryloxide derivatives and, in particular, of bis(cyclopentadienyl) zirconium diaryloxides, has been widely investigated. (Z 5 -C 5 Me 5 ) 2 Zr(OPh) 2 and (Z 5 -C 5 H 5 ) 2 Zr(OPh) 2 were synthesized by Howard et al, who investigated the nature of the zirconium-oxo interaction by structural analyses.…”