Synthesis, characterization, and reactivity of titanium(IV) complexes supported by proximally bridged p-tert-butylcalix[4]arene ligands

Oleg V. Ozerov; Nigam P. Rath; Folami T. Ladipo

doi:10.1016/S0022-328X(99)00279-X

Synthesis, characterization, and reactivity of titanium(IV) complexes supported by proximally bridged p-tert-butylcalix[4]arene ligands

Oleg V. Ozerov, Nigam P. Rath, Folami T. Ladipo

Chemistry

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

Treatment of dilithium or dipotassium salt of p-tert-butylcalix[4]arene with ^tBuPCl₂ or PhPCl₂ produced 1,2-alternate phosphorus-bridged p-tert-butylcalix[4]arene derivatives (^tBuPC)H₂ (1) and (PhPC)H₂ (2), respectively. An X-ray diffraction study of 2 showed that it exists in 1,2-alternate conformation. Reaction of 2 with sulfur gave (PhSPC)H₂ (3), which exists in cone conformation. Treatment of TiCl₄ with 1-3 produced the corresponding dichlorides L₂TiCl₂ [L₂=^tBuPC (5); PhPC (6); and PhSPC (7)]. Reaction of R₂Mg·2THF (R=Me or CH₂Ph) with (DMSC)TiCl₂ (8) yielded (DMSC)TiMe₂ (9) and (DMSC)Ti(CH₂Ph)₂ (10), respectively. Cationic derivatives [(DMSC)Ti(NCCH₃)Me₂]BAr^F₄ (11) and [(DMSC)Ti(NCCH₃)(CH₂Ph)]BAr^F₄ (12) were prepared from the respective reactions of 9 and 10 with [Ph₃C]BAr^F₄ [Ar^F=(CF₃)₂C₆H₃] in the presence of CH₃CN. Similarly, 9 and 10 reacted with [Ph₃C]OTf (one equivalent) to yield [(DMSC)Ti(OTf)Me₂] (13) and [(DMSC)Ti(OTf)(CH₂Ph)] (14), respectively. NMR data showed that the more exposed exo-alkyl was abstracted. Complexes 5-10 and 14 showed modest ethylene polymerization activities at 25°C with 500 molar equivalents of methylalumoxane (MAO) as cocatalyst.

Original language	English
Pages (from-to)	223-233
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	586
Issue number	2
DOIs	https://doi.org/10.1016/S0022-328X(99)00279-X
State	Published - Sep 5 1999

Bibliographical note

Funding Information:
Thanks are expressed to the Kentucky National Science Foundation EPSCoR Program (grant number EPS-9452895) for support of this work and to the Chemistry Department of the University of Kentucky for the award of fellowships to O.V.O. The authors also thank Professors Jack Selegue and Mark Meier for helpful discussions.

Keywords

Aryloxide ligand
Calix[4]arene ligand
Olefin polymerization
Titanium(IV)

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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title = "Synthesis, characterization, and reactivity of titanium(IV) complexes supported by proximally bridged p-tert-butylcalix[4]arene ligands",

abstract = "Treatment of dilithium or dipotassium salt of p-tert-butylcalix[4]arene with tBuPCl2 or PhPCl2 produced 1,2-alternate phosphorus-bridged p-tert-butylcalix[4]arene derivatives (tBuPC)H2 (1) and (PhPC)H2 (2), respectively. An X-ray diffraction study of 2 showed that it exists in 1,2-alternate conformation. Reaction of 2 with sulfur gave (PhSPC)H2 (3), which exists in cone conformation. Treatment of TiCl4 with 1-3 produced the corresponding dichlorides L2TiCl2 [L2=tBuPC (5); PhPC (6); and PhSPC (7)]. Reaction of R2Mg·2THF (R=Me or CH2Ph) with (DMSC)TiCl2 (8) yielded (DMSC)TiMe2 (9) and (DMSC)Ti(CH2Ph)2 (10), respectively. Cationic derivatives [(DMSC)Ti(NCCH3)Me2]BArF4 (11) and [(DMSC)Ti(NCCH3)(CH2Ph)]BArF4 (12) were prepared from the respective reactions of 9 and 10 with [Ph3C]BArF4 [ArF=(CF3)2C6H3] in the presence of CH3CN. Similarly, 9 and 10 reacted with [Ph3C]OTf (one equivalent) to yield [(DMSC)Ti(OTf)Me2] (13) and [(DMSC)Ti(OTf)(CH2Ph)] (14), respectively. NMR data showed that the more exposed exo-alkyl was abstracted. Complexes 5-10 and 14 showed modest ethylene polymerization activities at 25°C with 500 molar equivalents of methylalumoxane (MAO) as cocatalyst.",

keywords = "Aryloxide ligand, Calix[4]arene ligand, Olefin polymerization, Titanium(IV)",

author = "Ozerov, {Oleg V.} and Rath, {Nigam P.} and Ladipo, {Folami T.}",

note = "Funding Information: Thanks are expressed to the Kentucky National Science Foundation EPSCoR Program (grant number EPS-9452895) for support of this work and to the Chemistry Department of the University of Kentucky for the award of fellowships to O.V.O. The authors also thank Professors Jack Selegue and Mark Meier for helpful discussions. ",

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doi = "10.1016/S0022-328X(99)00279-X",

language = "English",

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T1 - Synthesis, characterization, and reactivity of titanium(IV) complexes supported by proximally bridged p-tert-butylcalix[4]arene ligands

AU - Ozerov, Oleg V.

AU - Rath, Nigam P.

AU - Ladipo, Folami T.

N1 - Funding Information: Thanks are expressed to the Kentucky National Science Foundation EPSCoR Program (grant number EPS-9452895) for support of this work and to the Chemistry Department of the University of Kentucky for the award of fellowships to O.V.O. The authors also thank Professors Jack Selegue and Mark Meier for helpful discussions.

PY - 1999/9/5

Y1 - 1999/9/5

N2 - Treatment of dilithium or dipotassium salt of p-tert-butylcalix[4]arene with tBuPCl2 or PhPCl2 produced 1,2-alternate phosphorus-bridged p-tert-butylcalix[4]arene derivatives (tBuPC)H2 (1) and (PhPC)H2 (2), respectively. An X-ray diffraction study of 2 showed that it exists in 1,2-alternate conformation. Reaction of 2 with sulfur gave (PhSPC)H2 (3), which exists in cone conformation. Treatment of TiCl4 with 1-3 produced the corresponding dichlorides L2TiCl2 [L2=tBuPC (5); PhPC (6); and PhSPC (7)]. Reaction of R2Mg·2THF (R=Me or CH2Ph) with (DMSC)TiCl2 (8) yielded (DMSC)TiMe2 (9) and (DMSC)Ti(CH2Ph)2 (10), respectively. Cationic derivatives [(DMSC)Ti(NCCH3)Me2]BArF4 (11) and [(DMSC)Ti(NCCH3)(CH2Ph)]BArF4 (12) were prepared from the respective reactions of 9 and 10 with [Ph3C]BArF4 [ArF=(CF3)2C6H3] in the presence of CH3CN. Similarly, 9 and 10 reacted with [Ph3C]OTf (one equivalent) to yield [(DMSC)Ti(OTf)Me2] (13) and [(DMSC)Ti(OTf)(CH2Ph)] (14), respectively. NMR data showed that the more exposed exo-alkyl was abstracted. Complexes 5-10 and 14 showed modest ethylene polymerization activities at 25°C with 500 molar equivalents of methylalumoxane (MAO) as cocatalyst.

AB - Treatment of dilithium or dipotassium salt of p-tert-butylcalix[4]arene with tBuPCl2 or PhPCl2 produced 1,2-alternate phosphorus-bridged p-tert-butylcalix[4]arene derivatives (tBuPC)H2 (1) and (PhPC)H2 (2), respectively. An X-ray diffraction study of 2 showed that it exists in 1,2-alternate conformation. Reaction of 2 with sulfur gave (PhSPC)H2 (3), which exists in cone conformation. Treatment of TiCl4 with 1-3 produced the corresponding dichlorides L2TiCl2 [L2=tBuPC (5); PhPC (6); and PhSPC (7)]. Reaction of R2Mg·2THF (R=Me or CH2Ph) with (DMSC)TiCl2 (8) yielded (DMSC)TiMe2 (9) and (DMSC)Ti(CH2Ph)2 (10), respectively. Cationic derivatives [(DMSC)Ti(NCCH3)Me2]BArF4 (11) and [(DMSC)Ti(NCCH3)(CH2Ph)]BArF4 (12) were prepared from the respective reactions of 9 and 10 with [Ph3C]BArF4 [ArF=(CF3)2C6H3] in the presence of CH3CN. Similarly, 9 and 10 reacted with [Ph3C]OTf (one equivalent) to yield [(DMSC)Ti(OTf)Me2] (13) and [(DMSC)Ti(OTf)(CH2Ph)] (14), respectively. NMR data showed that the more exposed exo-alkyl was abstracted. Complexes 5-10 and 14 showed modest ethylene polymerization activities at 25°C with 500 molar equivalents of methylalumoxane (MAO) as cocatalyst.

KW - Aryloxide ligand

KW - Calix[4]arene ligand

KW - Olefin polymerization

KW - Titanium(IV)

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

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ER -

Synthesis, characterization, and reactivity of titanium(IV) complexes supported by proximally bridged p-tert-butylcalix[4]arene ligands

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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