μ-Oxo-bis{isopropoxo[2,2′-(methylenedithio)bis(6-<i>tert</i>-butyl-4-methylphenolato)]titanium(IV)}

Centore, Roberto; Tuzi, Angela; Capacchione, Carmine; Oliva, Leone

doi:10.1107/s1600536806041419

Cited by 3 publications

(1 citation statement)

References 14 publications

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“…Benzene- d 6 , chloroform- d 1 , THF- d 8 , and other reagents were carefully dried and stored in a glovebox. The used bis(phenols) 1,3-dithiapropanediyl-bis(6- tert -butyl-4-methyl-phenol) (mtbmpH 2 ), 1,4-dithiabutanediyl-bis(6- tert -butyl-4-methyl-phenolato), (etbmpH 2 ), 1,4-dithiabutanediyl-bis(4,6-di- tert -butylphenol), (etbbpH 2 ), ,, and 1,4-dithiabutanediylbis(4,6-dicumyl-phenol) (etccpH 2 ) , were synthesized according to reported methods, as were trimethylindium and tris(trimethylsilylmethyl)indium …”

Section: Experimental Partmentioning

confidence: 99%

Indium Complexes Supported by 1,ω-Dithiaalkanediyl-Bridged Bis(phenolato) Ligands: Synthesis, Structure, and Controlled Ring-Opening Polymerization ofl-Lactide

Peckermann

Kapelski²,

Spaniol³

et al. 2009

Inorg. Chem.

103

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Indium bis(phenolato) complexes [In(L)R(THF)(n)] (L = 1,4-dithiabutanediylbis(4,6-di-tert-butylphenolato) (etbbp), R = Cl, n = 0, 1; L = 1,3-dithiapropanediylbis(6-tert-butyl-4-methylphenolato) (mtbmp), R = Me, n = 1, 2; L = 1,4-dithiabutanediyl-bis(6-tert-butyl-4-methyl-phenolato) (etbmp), R = Me, n = 0, 3; L = etbbp, R = CH(2)SiMe(3), n = 0, 4; L = 1,4-dithiabutanediylbis{4,6-di(2-phenyl-2-propyl)phenolato} (etccp), R = CH(2)SiMe(3), n = 0, 5) were prepared from indium trichloride or from the corresponding tris(alkyl) complexes and 1 equiv of tetradentate 1,omega-dithiaalkanediyl-bridged bis(phenol) LH(2). The monomeric nature of the alkyl indium complexes was shown by X-ray diffraction studies of the complexes [In(mtbmp)Me(THF)] (2), [In(etbbp)(CH(2)SiMe(3))] (4), and [In(etccp)(CH(2)SiMe(3))] (5). Pseudo-octahedral configuration was found for 2, while square pyramidal structure was observed for 4 and 5. The isopropoxy complexes [In(L)(O(i)Pr)] (L = etbbp, 6; etccp, 7) were synthesized starting with indium tris(isopropoxide). Complex 6 crystallized as homochiral dimer of pseudo-octahedral fragments with bridging mu(2)-alkoxide ligands, but in solution two diastereomers were observed. The isopropoxy complexes efficiently initiated the ring-opening polymerization of L-lactide in toluene to give isotactic poly(L-lactides) with narrow molecular weight distribution (M(w)/M(n) = 1.03-1.18).

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Section: Experimental Partmentioning

confidence: 99%

Indium Complexes Supported by 1,ω-Dithiaalkanediyl-Bridged Bis(phenolato) Ligands: Synthesis, Structure, and Controlled Ring-Opening Polymerization ofl-Lactide

Peckermann

Kapelski²,

Spaniol³

et al. 2009

Inorg. Chem.

103

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Enantiomerically Pure Titanium Complexes Containing an [OSSO]‐Type Bis(phenolate) Ligand: Synthesis, Structure, and Formation of Optically Active Oligostyrenes

Meppelder

Beckerle

Manivannan

et al. 2008

Chemistry An Asian Journal

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Chiral 1,2-trans-dithiocyclohexanediyl-bridged bis(phenols) of the type [2,2'-{HOC(6)H(2)-6-R(1)-4-R(2)}(2)S(2)C(6)H(10)] ([OSSO]H(2), R(1)=tBu, iPr, H; R(2)=tBu, iPr, Me) could be conveniently and selectively synthesized in three steps, starting from cyclohexene oxide and arene thiolate. The racemic bis(phenols) could be resolved using an enantiopure (S)-camphorsulfonic ester auxiliary or by (chiral) HPLC. Complexation of the racemic bis(phenols) to TiX(4) (X=Cl, OiPr) proceeds in a diastereoselective fashion to give only the Lambda,R,R and Delta,S,S enantiomers. Racemic [Ti{(OC(6)H(2)-6-tBu-4-Me)(2)S(2)C(6)H(10)}Cl(2)] reacts with benzyl magnesium bromide to afford the crystallographically characterized dibenzyl complex. The benzyl cation formed using B(C(6)F(5))(3) in C(6)D(5)Br slowly decomposes at temperatures above +10 degrees C. When treated with methylaluminoxane, the dichloro complexes [Ti{OSSO}Cl(2)] polymerize styrene with activities up to 146 kg (mol catalyst)(-1) [styrene (mol L(-1))](-1) h(-1); diisopropoxy complexes [Ti{OSSO}(OiPr)(2)] show mere trace activity. With 1-hexene as a chain-transfer agent, activated enantiopure titanium complexes give low-molecular-weight homochiral isotactic oligostyrenes, terminated by one to five 1-hexene units with M(n) values as low as 750 g mol(-1) for R=tBu and 1290 g mol(-1) for R=Me. Below M(n) approximately 5000 these oligostyrenes show optical activity.

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[OSSO]-bisphenolate metal complexes: A powerful and versatile tool in polymerization catalysis

Paradiso

Capaccio

Lamparelli

et al. 2021

Coordination Chemistry Reviews

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μ-Oxo-bis{isopropoxo[2,2′-(methylenedithio)bis(6-tert-butyl-4-methylphenolato)]titanium(IV)}

Abstract: Key indicatorsSingle-crystal X-ray study T = 173 K Mean (C-C) = 0.005 Å Disorder in main residue R factor = 0.054 wR factor = 0.139 Data-to-parameter ratio = 21.2 For details of how these key indicators were automatically derived from the article, see

Cited by 3 publications

References 14 publications

Indium Complexes Supported by 1,ω-Dithiaalkanediyl-Bridged Bis(phenolato) Ligands: Synthesis, Structure, and Controlled Ring-Opening Polymerization ofl-Lactide

Indium Complexes Supported by 1,ω-Dithiaalkanediyl-Bridged Bis(phenolato) Ligands: Synthesis, Structure, and Controlled Ring-Opening Polymerization ofl-Lactide

Enantiomerically Pure Titanium Complexes Containing an [OSSO]‐Type Bis(phenolate) Ligand: Synthesis, Structure, and Formation of Optically Active Oligostyrenes

[OSSO]-bisphenolate metal complexes: A powerful and versatile tool in polymerization catalysis

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