Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride)

Seok Kyun Noh; Gyu gum Byun; Chul soo Lee; Dongho Lee; Keun byung Yoon; Kyoung Seok Kang

doi:10.1016/0022-328X(96)06128-1

Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride)

Seok Kyun Noh
, Gyu gum Byun
, Chul soo Lee
, Dongho Lee
, Keun byung Yoon
, Kyoung Seok Kang

Yeungnam University
Kyungpook National University
Hanwha

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

48 Scopus citations

Abstract

The reaction of dithallium salts of tetramethyldisiloxanediylbis(cyclopentadienyl), 3, and hexamethyltrisiloxanediylbis(cyclopentadienyl), 4, with two equivalents of TiCl₄ gives the title compounds tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride), 5 and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride), 6 respectively. The stoichiometric reaction of 5 and 6 with water results in the formation of new oxygen-bridged metallocenes [(TiCl₂)₂(μ²-O)-(η⁵-C₅H₄)₂-μ²-(SiMe₂)₂O], 7, and [(TiCl₂)₂(μ²-O)-(η⁵-C₅H₄)₂-μ²-(SiMe₂)₃O₂}], 8. In addition, further reaction of 7 and 8 with another one equivalent of water or the treatment of 5 and 6 with an excess amount of water gives rise to the formation of the metallocene compounds having Ti₄O₄ rings [(TiCl)₂(μ²-O)-(η⁵-C₅H₄)₂-μ²-(SiMe₂)₂O]₂(μ²-O)₂, 9, and [(TiCl)₂(μ²-O)-(η⁵-C₅H₄)₂-μ²-(SiMe₂)₃O₂]₂(μ²-O)₂, 10. All the new kinds of metallocenes prepared have been characterized by IR, NMR, mass spectrometry, or elemental analysis. Especially an investigation of the Δδ values in ¹H NMR and a comparison between the theoretical and observed isotopic ratio in a mass spectra among the synthesized bridged compounds have been very conveniently utilized to study their structures. Polymerization experiments with the dinuclear complexes in the presence of methylaluminoxane as a cocatalyst indicate that the compounds 5 and 6 do exhibit catalytic activity for syndiotactic polymerization of styrene.

Original language	English
Pages (from-to)	1-6
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	518
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(96)06128-1
State	Published - 12 Jul 1996

Keywords

Binuclear
Metallocene
Oxygen bridge
Polysiloxane
Silicon

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Noh, S. K., Byun, G. G., Lee, C. S., Lee, D., Yoon, K. B., & Kang, K. S. (1996). Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride). Journal of Organometallic Chemistry, 518(1-2), 1-6. https://doi.org/10.1016/0022-328X(96)06128-1

@article{dd8429be05694da28107fea0c1653212,

title = "Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride)",

abstract = "The reaction of dithallium salts of tetramethyldisiloxanediylbis(cyclopentadienyl), 3, and hexamethyltrisiloxanediylbis(cyclopentadienyl), 4, with two equivalents of TiCl4 gives the title compounds tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride), 5 and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride), 6 respectively. The stoichiometric reaction of 5 and 6 with water results in the formation of new oxygen-bridged metallocenes [(TiCl2)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)2O], 7, and [(TiCl2)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)3O2\}], 8. In addition, further reaction of 7 and 8 with another one equivalent of water or the treatment of 5 and 6 with an excess amount of water gives rise to the formation of the metallocene compounds having Ti4O4 rings [(TiCl)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)2O]2(μ2-O)2, 9, and [(TiCl)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)3O2]2(μ2-O)2, 10. All the new kinds of metallocenes prepared have been characterized by IR, NMR, mass spectrometry, or elemental analysis. Especially an investigation of the Δδ values in 1H NMR and a comparison between the theoretical and observed isotopic ratio in a mass spectra among the synthesized bridged compounds have been very conveniently utilized to study their structures. Polymerization experiments with the dinuclear complexes in the presence of methylaluminoxane as a cocatalyst indicate that the compounds 5 and 6 do exhibit catalytic activity for syndiotactic polymerization of styrene.",

keywords = "Binuclear, Metallocene, Oxygen bridge, Polysiloxane, Silicon",

author = "Noh, \{Seok Kyun\} and Byun, \{Gyu gum\} and Lee, \{Chul soo\} and Dongho Lee and Yoon, \{Keun byung\} and Kang, \{Kyoung Seok\}",

year = "1996",

month = jul,

day = "12",

doi = "10.1016/0022-328X(96)06128-1",

language = "English",

volume = "518",

pages = "1--6",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

Noh, SK, Byun, GG, Lee, CS, Lee, D, Yoon, KB & Kang, KS 1996, 'Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride)', Journal of Organometallic Chemistry, vol. 518, no. 1-2, pp. 1-6. https://doi.org/10.1016/0022-328X(96)06128-1

Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride). / Noh, Seok Kyun; Byun, Gyu gum; Lee, Chul soo et al.
In: Journal of Organometallic Chemistry, Vol. 518, No. 1-2, 12.07.1996, p. 1-6.

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

TY - JOUR

T1 - Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride)

AU - Noh, Seok Kyun

AU - Byun, Gyu gum

AU - Lee, Chul soo

AU - Lee, Dongho

AU - Yoon, Keun byung

AU - Kang, Kyoung Seok

PY - 1996/7/12

Y1 - 1996/7/12

N2 - The reaction of dithallium salts of tetramethyldisiloxanediylbis(cyclopentadienyl), 3, and hexamethyltrisiloxanediylbis(cyclopentadienyl), 4, with two equivalents of TiCl4 gives the title compounds tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride), 5 and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride), 6 respectively. The stoichiometric reaction of 5 and 6 with water results in the formation of new oxygen-bridged metallocenes [(TiCl2)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)2O], 7, and [(TiCl2)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)3O2}], 8. In addition, further reaction of 7 and 8 with another one equivalent of water or the treatment of 5 and 6 with an excess amount of water gives rise to the formation of the metallocene compounds having Ti4O4 rings [(TiCl)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)2O]2(μ2-O)2, 9, and [(TiCl)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)3O2]2(μ2-O)2, 10. All the new kinds of metallocenes prepared have been characterized by IR, NMR, mass spectrometry, or elemental analysis. Especially an investigation of the Δδ values in 1H NMR and a comparison between the theoretical and observed isotopic ratio in a mass spectra among the synthesized bridged compounds have been very conveniently utilized to study their structures. Polymerization experiments with the dinuclear complexes in the presence of methylaluminoxane as a cocatalyst indicate that the compounds 5 and 6 do exhibit catalytic activity for syndiotactic polymerization of styrene.

AB - The reaction of dithallium salts of tetramethyldisiloxanediylbis(cyclopentadienyl), 3, and hexamethyltrisiloxanediylbis(cyclopentadienyl), 4, with two equivalents of TiCl4 gives the title compounds tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride), 5 and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride), 6 respectively. The stoichiometric reaction of 5 and 6 with water results in the formation of new oxygen-bridged metallocenes [(TiCl2)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)2O], 7, and [(TiCl2)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)3O2}], 8. In addition, further reaction of 7 and 8 with another one equivalent of water or the treatment of 5 and 6 with an excess amount of water gives rise to the formation of the metallocene compounds having Ti4O4 rings [(TiCl)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)2O]2(μ2-O)2, 9, and [(TiCl)2(μ2-O)-(η5-C5H4)2-μ2-(SiMe2)3O2]2(μ2-O)2, 10. All the new kinds of metallocenes prepared have been characterized by IR, NMR, mass spectrometry, or elemental analysis. Especially an investigation of the Δδ values in 1H NMR and a comparison between the theoretical and observed isotopic ratio in a mass spectra among the synthesized bridged compounds have been very conveniently utilized to study their structures. Polymerization experiments with the dinuclear complexes in the presence of methylaluminoxane as a cocatalyst indicate that the compounds 5 and 6 do exhibit catalytic activity for syndiotactic polymerization of styrene.

KW - Binuclear

KW - Metallocene

KW - Oxygen bridge

KW - Polysiloxane

KW - Silicon

UR - https://www.scopus.com/pages/publications/0030581032

U2 - 10.1016/0022-328X(96)06128-1

DO - 10.1016/0022-328X(96)06128-1

M3 - Article

AN - SCOPUS:0030581032

SN - 0022-328X

VL - 518

SP - 1

EP - 6

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Noh SK, Byun GG, Lee CS, Lee D, Yoon KB, Kang KS. Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride). Journal of Organometallic Chemistry. 1996 Jul 12;518(1-2):1-6. doi: 10.1016/0022-328X(96)06128-1

Synthesis, characterization, and reactivities of the polysiloxane-bridged binuclear metallocenes tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride) and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride)

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