31011-57-1Relevant articles and documents
A Simple Synthesis of 3,3-Diphenylcyclopropene
Nizovtsev, Alexey V.
, p. 537 - 542 (2020/09/09)
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Bis(arylimino)pyridine derivatives of Group 4 metals: Preparation, characterization and activity in ethylene polymerization
Calderazzo, Fausto,Englert, Ulli,Pampaloni, Guido,Santi, Roberto,Sommazzi, Anna,Zinna, Marianna
, p. 914 - 922 (2007/10/03)
Titanium tetrachloride reacts with 2,6-bis[(1-phenylimino)ethyl]pyridine, 1, and 2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine, 2, giving the adducts of general formulae [Ti(1)Cl3]Cl, 3, and [Ti(2)Cl 3]Cl, 6, the latter through the intermediacy of the covalently bonded [Ti(2)Cl4], 4. Heating 6 leads to reduction to the titanium(III) derivative [Ti(2)Cl3], 12, the latter characterized by X-ray diffraction methods. The reaction of [Ti(1)Cl3]Cl with a toluene solution of MAO proceeds with methylation at the ortho-position of the pyridine ring to give the titanium(IV) derivative [Ti(C22H21N 3)Cl3], 8. The reaction of [Ti(2)Cl3]Cl with MAO gives a mixture of products containing [Ti(2)Cl2(OAlCl 3)], 9. Compound 9, which has been prepared independently by reacting 6 with AlOCl, is a rare case of a compound containing the -OAlCl3 moiety, as shown by a single-crystal X-ray diffraction study. From the tetrachlorides of zirconium and hafnium with 1 or 2, the corresponding adducts [M(L)Cl4] have been obtained in high yields. These derivatives of Group 4 metals act as ethylene polymerization catalytic precursors: the substitution of the phenyl ring of the imino fragment strongly influences the catalytic activity which is 5,544 kgPE molTi-1 h-1 in the case of 3 and 267 kgPE molTi -1 h-1 with 6. Catalytic activity has been observed for zirconium and hafnium too, the activity decreasing from zirconium to hafnium, under comparable conditions. The Royal Society of Chemistry 2005.
Synthesis and characterization of titanium(IV) complexes containing the diphenylphosphino- and diphenylthiophosphoryl-functionalized cyclopentadienyl ligand. Crystal and molecular structure of Ti(η5-C5H4PPh2)Cl3
Flores, Juan C.,Hernández, Rocío,Royo, Pascual,Butt, Angelika,Spaniol, Thomas P.,Okuda, Jun
, p. 202 - 210 (2007/10/03)
The trimethylsilyl cyclopentadiene derivative C5H4(SiMe3)PPh2 (1) was treated with TiCl4 to give the air- and moisture-sensitive mono(cyclopentadienyl) compound Ti(η5-C5H4PPh2)Cl3 (4). Reaction of 4 with Mg(CH2C6H5)2(THF)2 gave Ti(η5-C5H4PPh2)(CH2C6H5)3 (5). Reactions of the lithium and thallium derivatives M{C5H4P(S)Ph2} (M=Li (2), Tl (3)) with one equiv. of TiCl4 afforded the mono(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}Cl3 (6), whereas reaction with 0.5 equiv. of TiCl4 gave the bis(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}2Cl2 (8). Compound 6 was also isolated as a minor product from the reaction of Ti{η5-C5H4P(S)Ph2}2Cl2 (8) with one equiv. of TiCl4. The major product was identified as an inseparable mixture of two compounds [Ti{η5-C5H4P(S)Ph2}2Cl2·TiCl4]n (7a and 7b). Reaction of Ti(η5-C5H5)Cl3 with 3 afforded the `mixed-ring' bis(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}(η5-C5H5)Cl2 (9). Compounds 6-9 are very moisture-sensitive and easily decompose to form the cyclopentadiene C5H5P(S)Ph2. Structural data of these complexes indicate η5-coordination of the substituted cyclopentadienyl ligands and this coordination mode was confirmed by X-ray crystal structure analysis of compound 4.
