0000000001308141
AUTHOR
Hak-chul Kang
Synthesis and structural characterization of titanium complexes containing a sulfinyl-bridged bis(phenolato) ligand
Abstract Titanium complexes containing the novel tridentate 2,2′-sulfinylbis(6-tert-butyl-4-methylphenoxo) ligand (sibmp) were synthesized and characterized. Treatment of titanium tetra-iso-propoxide with 2,2′-sulfinylbis(6-tert-4-methylphenol) (sibmpH2) in 1:1 molar ratio afforded red-orange, sparingly soluble di-iso-propoxo derivative [Ti(sibmp)(O-i-Pr)2]2·0.5 Et2O. The single-crystal structure analysis was performed and revealed a dimeric centrosymmetric structure with a planar Ti2O2 core. The titanium center is approximately octahedral with a SO function intramolecularly coordinated at the titanium center. Treatment of sibmpH2 with titanium tetra-iso-propoxide in 2:1 molar ratio gave y…
Aluminum complexes of sterically hindered tetradentate Schiff bases: Synthesis, structure, and reactivity toward ɛ-caprolactone
Abstract The sterically hindered Schiff bases tbmSalenH2 [tbmSalen = N,N′-1,2-ethylenebis(3-tert-butyl-5-methylsalicylideneimine)] and tbmSalcenH2 [tbmSalcen = N,N′-trans-1,2-cyclohexanediyl-bis(3-tert-butyl-5-methylsalicylideneimine)] afforded a series of aluminum complexes of the general formulae [Al(tbmSalen)X] and [Al(tbmSalcen)X] (X = Cl, Me, Et). The molecular structure of [Al(tbmSalcen)Cl] was determined by single-crystal X-ray structural analysis which revealed a five-coordinate aluminum center with a distorted square pyramidal geometry. The alkyl complexes were found to oligomerize ɛ-caprolactone.
Titanium Complexes of Chelating Bis(phenolato) Ligands with Long Titanium−Sulfur Bonds. A Novel Type of Ancillary Ligand for Olefin Polymerization Catalysts
The sulfide-linked bis(phenol) tbmpH2 (tbmp = 2,2‘-thiobis(6-tert-butyl-4-methylphenolato)) gives a series of titanium complexes of the formula [Ti(tbmp)X2]2 or [Ti(tbmp)(L)X2] (L = two-electron ligand, X = one-electron ligand). The molecular structures of [Ti(tbmp)(OiPr)2]2 and of [Ti(tbmp){C6H4(CH2NMe2)-2}Cl] were determined by single-crystal X-ray structural analyses. An unusually long titanium−sulfur bond of ∼270 pm is observed in both complexes which contain a six-coordinate titanium center. Variable-temperature NMR spectroscopy shows a fluxional coordination of the chelating aryl group in [Ti(tbmp){C6H4(CH2NMe2)-2}Cl].
Alcoholysis of Aluminum Alkyls Supported by Bulky Phenoxide Ligands: Synthesis, Characterization, and ε-Caprolactone Polymerization Activity of Two Dimeric Aluminum Isopropoxides
Reaction of trialkylaluminum Al2R6 (R = Me, Et) with 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (mbmpH2) gives the dimeric mono(alkyl) complex [Al(mbmp)R]2 with bridging oxygen atoms. Reaction of [Al(mbmp)R]2 with one equiv. of 2-propanol results in the formation of the dimeric isopropoxide [Al(mbmp)(μ-OiPr)]2. Single-crystal X-ray analysis shows a C2h-symmetric structure with a planar Al2O2 core. Monomeric methylbis(2,6-di-tert-butyl-4-methylphenolato)aluminum, AlMe(OC6H2-2,6-tBu2-4-Me)2 (MAD), was found to react with one equiv. of 2-propanol to give a dimeric isopropoxide [AlMe(OC6H2-2,6-tBu2-4-Me)(μ-OiPr)]2 in which the bulky phenolate, instead of the methyl group, has been displaced…
CCDC 104970: Experimental Crystal Structure Determination
Related Article: I.Taden, Hak-Chul Kang, W.Massa, T.P.Spaniol, J.Okuda|2000|Eur.J.Inorg.Chem.||441|doi:10.1002/(SICI)1099-0682(200003)2000:3<441::AID-EJIC441>3.0.CO;2-M
CCDC 133689: Experimental Crystal Structure Determination
Related Article: I.Taden, Hak-Chul Kang, W.Massa, T.P.Spaniol, J.Okuda|2000|Eur.J.Inorg.Chem.||441|doi:10.1002/(SICI)1099-0682(200003)2000:3<441::AID-EJIC441>3.0.CO;2-M