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Tetrabenzo[a,c,g,i]fluorenyltitanium(III) and -(IV) complexes: Syntheses, reactions, and catalytic application
Schroeder, K., Haase, D., Saak, W., Beckhaus, R., Kretschmer, W. P. & Luetzen, A., 28-Apr-2008, In : Organometallics. 27, 8, p. 1859-1868 10 p.Research output: Contribution to journal › Article › Academic › peer-review
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Tetrabenzo[a,c,g,i]fluorenyltitanium(III) and -(IV) complexes: Syntheses, reactions, and catalytic application. / Schroeder, Kai; Haase, Detlev; Saak, Wolfgang; Beckhaus, Ruediger; Kretschmer, Winfried P.; Luetzen, Arne.
In: Organometallics, Vol. 27, No. 8, 28.04.2008, p. 1859-1868.Research output: Contribution to journal › Article › Academic › peer-review
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TY - JOUR
T1 - Tetrabenzo[a,c,g,i]fluorenyltitanium(III) and -(IV) complexes: Syntheses, reactions, and catalytic application
AU - Schroeder, Kai
AU - Haase, Detlev
AU - Saak, Wolfgang
AU - Beckhaus, Ruediger
AU - Kretschmer, Winfried P.
AU - Luetzen, Arne
PY - 2008/4/28
Y1 - 2008/4/28
N2 - Reacting tetrabenzo[a,c,g,i]fluorenyllithium {TbfLi(THF)(4) (1)} with TiCl(3)(THF)(3) (2) leads to the formation of the eta(5)-tetrabenzo[a,c,g,i]fluorenyltitanium(III) derivative TbfTiCl(2)(THF) (3), which can be conveyed to the titanium(IV)complex TbfTiCl(3) (4) by oxidative chlorination with CCl(4). Subsequent reaction with various lithium phenoxides gives a series of titanium complexes of the type TbtTiCl(2)(OAr) (Ar = 4-(t)BUC(6)H(4) (5), 2,6-Me(2)C(6)H(3) (6), 2,4,6-Me(3)C(6)H(2) (7), 2,6-(i)PrC(6)H(3) (8), 2,6-Ph(2)C(6)H(3) (9)). Furthermore, 3 was reacted with radicals or radical-generating peroxides to form the complexes TbfTiCl(2)TEMPO (10) and TbfTiCl(2)O(t)Bu (11). All compounds were characterized by IR, MS, and NMR measurements and X-ray crystallography. Finally, compounds 6, 8, 9, and 10 were subjected to ethylene polymerization experiments using d-MAO. The activities increase in the following order [kG(PE)mol(Ti)(-1) h(-1) bar(-1)]: 6 (320) <8 (320) <10 (760) <9 (1000).
AB - Reacting tetrabenzo[a,c,g,i]fluorenyllithium {TbfLi(THF)(4) (1)} with TiCl(3)(THF)(3) (2) leads to the formation of the eta(5)-tetrabenzo[a,c,g,i]fluorenyltitanium(III) derivative TbfTiCl(2)(THF) (3), which can be conveyed to the titanium(IV)complex TbfTiCl(3) (4) by oxidative chlorination with CCl(4). Subsequent reaction with various lithium phenoxides gives a series of titanium complexes of the type TbtTiCl(2)(OAr) (Ar = 4-(t)BUC(6)H(4) (5), 2,6-Me(2)C(6)H(3) (6), 2,4,6-Me(3)C(6)H(2) (7), 2,6-(i)PrC(6)H(3) (8), 2,6-Ph(2)C(6)H(3) (9)). Furthermore, 3 was reacted with radicals or radical-generating peroxides to form the complexes TbfTiCl(2)TEMPO (10) and TbfTiCl(2)O(t)Bu (11). All compounds were characterized by IR, MS, and NMR measurements and X-ray crystallography. Finally, compounds 6, 8, 9, and 10 were subjected to ethylene polymerization experiments using d-MAO. The activities increase in the following order [kG(PE)mol(Ti)(-1) h(-1) bar(-1)]: 6 (320) <8 (320) <10 (760) <9 (1000).
KW - NONBRIDGED HALF-TITANOCENES
KW - RING-OPENING POLYMERIZATION
KW - OLEFIN POLYMERIZATION
KW - ORGANOMETALLIC CHEMISTRY
KW - STYRENE POLYMERIZATION
KW - MOLECULAR-STRUCTURE
KW - CRYSTAL-STRUCTURE
KW - METAL-COMPLEXES
KW - CYCLOPENTADIENYL
KW - LIGAND
U2 - 10.1021/om7012293
DO - 10.1021/om7012293
M3 - Article
VL - 27
SP - 1859
EP - 1868
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 8
ER -
ID: 1978688