Synthesis, hydrosilylation reactivity and catalytic properties of group 4 ansa-metallocene complexes

Santiago Gómez-Ruiz; Sanjiv Prashar; Mariano Fajardo; Antonio Antiñolo; Antonio Otero; Miguel A. Maestro; Victoria Volkis; Moris S. Eisen; César J. Pastor

doi:10.1016/j.poly.2005.03.056

Synthesis, hydrosilylation reactivity and catalytic properties of group 4 ansa-metallocene complexes

Santiago Gómez-Ruiz, Sanjiv Prashar^*, Mariano Fajardo, Antonio Antiñolo, Antonio Otero, Miguel A. Maestro, Victoria Volkis, Moris S. Eisen, César J. Pastor

^*Corresponding author for this work

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

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Abstract

The following ansa-ligand precursors, Et(H)Si(C₅H ₅)₂ (1), Et(H)Si(C₅HMe₄)Cl (2), Et(H)Si(C₅HMe₄)(C₅H₅) (3), Ph(H)Si(C₅HMe₄)Cl (4), Ph(H)Si(C₅HMe ₄)(C₅H₅) (5), Ph(H)Si(C₅HMe ₄)₂ (6), CH₂CHCH₂(H)Si(C ₅HMe₄)Cl (7), CH₂CHCH₂(H)Si(C ₅HMe₄)(C₅H₅) (8), CH ₂CHCH₂(H)Si(C₅HMe₄)₂ (9), and their lithium derivatives, Li₂{Et(H)Si(C₅H ₄)₂} (10), Li₂{Et(H)Si(C₅Me ₄)(C₅H₄)} (11), Li₂{Ph(H)Si(C ₅Me₄)(C₅H₄)} (12), Li ₂{Ph(H)Si(C₅Me₄)₂} (13), Li ₂{CH₂CHCH₂(H)Si(C₅Me ₄)(C₅H₄)} (14) and Li₂{CH ₂CHCH₂(H)Si(C₅Me₄)₂} (15) have been prepared. The group 4 metal complexes, [M{Et(H)Si(η⁵- C₅H₄)₂}Cl₂] (M = Ti (16a), Zr (16b), Hf (16c)), [M{Et(H)Si(η⁵-C₅Me₄) (η⁵-C₅H₄)}Cl₂] (M = Ti (17a), Zr (17b), Hf (17c)), [M{Ph(H)Si(η⁵-C₅Me ₄)(η⁵-C₅H₄)}Cl₂] (M = Ti (18a), Zr (18b), Hf (18c)), [M{Ph(H)Si(η⁵-C ₅Me₄)₂}Cl₂] (M = Ti(19a), Zr (19b), Hf (19c)), M{CH₂CHCH₂(H)Si(η⁵-C ₅Me₄)(η⁵-C₅H₄)} Cl₂] (M = Ti (20a), Zr (20b)) and [M{CH₂CHCH ₂(H)Si(η⁵-C₅Me₄) ₂}Cl₂] (M = Ti (21a), Zr (21b), Hf (21c)) were synthesized from the reaction of the lithium ansa-derivatives and the tetrachloride salts of the transition metal. The reactivity of the group 4 metal complexes in hydrosilylation processes has been studied. The reaction of 16b, 17a and 17b with tetravinylsilane gave [Zr{(CH₂CH)₃SiCH ₂CH₂(Et)Si(η⁵-C₅H ₄)₂}Cl₂] (22b) and [M{(CH₂CH) ₃SiCH₂CH₂(Et)Si(η⁵-C ₅Me₄)(η⁵-C₅H₄)} Cl₂] (M = Ti (23a), Zr (23b)), respectively. The reaction of 17a and 17b with dimethyldivinylsilane yielded the hydrosilylation products [M{(CH ₂CH)Me₂SiCH₂CH₂(Et) Si(η⁵-C₅Me₄)(η⁵-C ₅H₄)}Cl₂] (M = Ti (24a), Zr (24b)), respectively. 23b and 24b reacted with the silane reagent HSiEt₃ to form, via hydrosilylation, [Zr{(Et₃SiCH₂CH ₂)₃SiCH₂CH₂(Et)Si(η⁵- C₅Me₄)(η⁵-C₅H ₄)}Cl₂] (25b) and [Zr{(Et₃SiCH ₂CH₂)Me₂SiCH₂CH₂(Et) Si(η⁵-C₅Me₄)(η⁵-C ₅H₄)}Cl₂] (26b), respectively. The previously synthesized compounds, [M{CH₂CH(Me)Si(η⁵-C ₅Me₄)₂}Cl₂] (M = Ti (27a), Zr (27b)) and [Zr{CH₂CHCH₂(Me)Si(η⁵-C ₅Me₄)₂}Cl₂] (28b), have also been tested in reactions of hydrosilylation with SiHMeCl₂ to give [M{Cl₂MeSiCH₂CH₂(Me)Si(η⁵- C₅Me₄)₂}Cl₂] (M = Ti (29a), Zr (29b)) and [Zr{Cl₂MeSiCH₂CH₂CH ₂(Me)Si(η⁵-C₅Me₄) ₂}Cl₂] (30b). All the zirconocene compounds are active to varying degrees as catalysts in the polymerization of ethylene. The molecular structures of 21b and 21c have been determined by single crystal X-ray diffraction studies.

Original language	English
Pages (from-to)	1298-1313
Number of pages	16
Journal	Polyhedron
Volume	24
Issue number	11
DOIs	https://doi.org/10.1016/j.poly.2005.03.056
State	Published - 4 Aug 2005
Externally published	Yes

Keywords

Hafnium
Hydrosilylation
Polymerization
Titanium
Zirconium
ansa-Metallocene complexes

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10.1016/j.poly.2005.03.056

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@article{6ea74f3cc7444e138b9db51f4ca76469,

title = "Synthesis, hydrosilylation reactivity and catalytic properties of group 4 ansa-metallocene complexes",

abstract = "The following ansa-ligand precursors, Et(H)Si(C5H 5)2 (1), Et(H)Si(C5HMe4)Cl (2), Et(H)Si(C5HMe4)(C5H5) (3), Ph(H)Si(C5HMe4)Cl (4), Ph(H)Si(C5HMe 4)(C5H5) (5), Ph(H)Si(C5HMe 4)2 (6), CH2CHCH2(H)Si(C 5HMe4)Cl (7), CH2CHCH2(H)Si(C 5HMe4)(C5H5) (8), CH 2CHCH2(H)Si(C5HMe4)2 (9), and their lithium derivatives, Li2{Et(H)Si(C5H 4)2} (10), Li2{Et(H)Si(C5Me 4)(C5H4)} (11), Li2{Ph(H)Si(C 5Me4)(C5H4)} (12), Li 2{Ph(H)Si(C5Me4)2} (13), Li 2{CH2CHCH2(H)Si(C5Me 4)(C5H4)} (14) and Li2{CH 2CHCH2(H)Si(C5Me4)2} (15) have been prepared. The group 4 metal complexes, [M{Et(H)Si(η5- C5H4)2}Cl2] (M = Ti (16a), Zr (16b), Hf (16c)), [M{Et(H)Si(η5-C5Me4) (η5-C5H4)}Cl2] (M = Ti (17a), Zr (17b), Hf (17c)), [M{Ph(H)Si(η5-C5Me 4)(η5-C5H4)}Cl2] (M = Ti (18a), Zr (18b), Hf (18c)), [M{Ph(H)Si(η5-C 5Me4)2}Cl2] (M = Ti(19a), Zr (19b), Hf (19c)), M{CH2CHCH2(H)Si(η5-C 5Me4)(η5-C5H4)} Cl2] (M = Ti (20a), Zr (20b)) and [M{CH2CHCH 2(H)Si(η5-C5Me4) 2}Cl2] (M = Ti (21a), Zr (21b), Hf (21c)) were synthesized from the reaction of the lithium ansa-derivatives and the tetrachloride salts of the transition metal. The reactivity of the group 4 metal complexes in hydrosilylation processes has been studied. The reaction of 16b, 17a and 17b with tetravinylsilane gave [Zr{(CH2CH)3SiCH 2CH2(Et)Si(η5-C5H 4)2}Cl2] (22b) and [M{(CH2CH) 3SiCH2CH2(Et)Si(η5-C 5Me4)(η5-C5H4)} Cl2] (M = Ti (23a), Zr (23b)), respectively. The reaction of 17a and 17b with dimethyldivinylsilane yielded the hydrosilylation products [M{(CH 2CH)Me2SiCH2CH2(Et) Si(η5-C5Me4)(η5-C 5H4)}Cl2] (M = Ti (24a), Zr (24b)), respectively. 23b and 24b reacted with the silane reagent HSiEt3 to form, via hydrosilylation, [Zr{(Et3SiCH2CH 2)3SiCH2CH2(Et)Si(η5- C5Me4)(η5-C5H 4)}Cl2] (25b) and [Zr{(Et3SiCH 2CH2)Me2SiCH2CH2(Et) Si(η5-C5Me4)(η5-C 5H4)}Cl2] (26b), respectively. The previously synthesized compounds, [M{CH2CH(Me)Si(η5-C 5Me4)2}Cl2] (M = Ti (27a), Zr (27b)) and [Zr{CH2CHCH2(Me)Si(η5-C 5Me4)2}Cl2] (28b), have also been tested in reactions of hydrosilylation with SiHMeCl2 to give [M{Cl2MeSiCH2CH2(Me)Si(η5- C5Me4)2}Cl2] (M = Ti (29a), Zr (29b)) and [Zr{Cl2MeSiCH2CH2CH 2(Me)Si(η5-C5Me4) 2}Cl2] (30b). All the zirconocene compounds are active to varying degrees as catalysts in the polymerization of ethylene. The molecular structures of 21b and 21c have been determined by single crystal X-ray diffraction studies.",

keywords = "Hafnium, Hydrosilylation, Polymerization, Titanium, Zirconium, ansa-Metallocene complexes",

author = "Santiago G{\'o}mez-Ruiz and Sanjiv Prashar and Mariano Fajardo and Antonio Anti{\~n}olo and Antonio Otero and Maestro, {Miguel A.} and Victoria Volkis and Eisen, {Moris S.} and Pastor, {C{\'e}sar J.}",

note = "Funding Information: We gratefully acknowledge financial support from the Ministerio de Educaci{\'o}n y Ciencia, Spain (Grants No. BQU2002-04638-C02-01 and MAT2003-05345), the Junta de Comunidades de Castilla-La Mancha (PAC-02-003 and PAI-02-010), the Comunidad de Madrid (GR/MAT/0929/2004) and the Universidad Rey Juan Carlos (GVC-2004-12). We also thank Repsol-YPF for their assistance in the polymer analysis. ",

year = "2005",

month = aug,

day = "4",

doi = "10.1016/j.poly.2005.03.056",

language = "英语",

volume = "24",

pages = "1298--1313",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd.",

number = "11",

}

TY - JOUR

T1 - Synthesis, hydrosilylation reactivity and catalytic properties of group 4 ansa-metallocene complexes

AU - Gómez-Ruiz, Santiago

AU - Prashar, Sanjiv

AU - Fajardo, Mariano

AU - Antiñolo, Antonio

AU - Otero, Antonio

AU - Maestro, Miguel A.

AU - Volkis, Victoria

AU - Eisen, Moris S.

AU - Pastor, César J.

N1 - Funding Information: We gratefully acknowledge financial support from the Ministerio de Educación y Ciencia, Spain (Grants No. BQU2002-04638-C02-01 and MAT2003-05345), the Junta de Comunidades de Castilla-La Mancha (PAC-02-003 and PAI-02-010), the Comunidad de Madrid (GR/MAT/0929/2004) and the Universidad Rey Juan Carlos (GVC-2004-12). We also thank Repsol-YPF for their assistance in the polymer analysis.

PY - 2005/8/4

Y1 - 2005/8/4

N2 - The following ansa-ligand precursors, Et(H)Si(C5H 5)2 (1), Et(H)Si(C5HMe4)Cl (2), Et(H)Si(C5HMe4)(C5H5) (3), Ph(H)Si(C5HMe4)Cl (4), Ph(H)Si(C5HMe 4)(C5H5) (5), Ph(H)Si(C5HMe 4)2 (6), CH2CHCH2(H)Si(C 5HMe4)Cl (7), CH2CHCH2(H)Si(C 5HMe4)(C5H5) (8), CH 2CHCH2(H)Si(C5HMe4)2 (9), and their lithium derivatives, Li2{Et(H)Si(C5H 4)2} (10), Li2{Et(H)Si(C5Me 4)(C5H4)} (11), Li2{Ph(H)Si(C 5Me4)(C5H4)} (12), Li 2{Ph(H)Si(C5Me4)2} (13), Li 2{CH2CHCH2(H)Si(C5Me 4)(C5H4)} (14) and Li2{CH 2CHCH2(H)Si(C5Me4)2} (15) have been prepared. The group 4 metal complexes, [M{Et(H)Si(η5- C5H4)2}Cl2] (M = Ti (16a), Zr (16b), Hf (16c)), [M{Et(H)Si(η5-C5Me4) (η5-C5H4)}Cl2] (M = Ti (17a), Zr (17b), Hf (17c)), [M{Ph(H)Si(η5-C5Me 4)(η5-C5H4)}Cl2] (M = Ti (18a), Zr (18b), Hf (18c)), [M{Ph(H)Si(η5-C 5Me4)2}Cl2] (M = Ti(19a), Zr (19b), Hf (19c)), M{CH2CHCH2(H)Si(η5-C 5Me4)(η5-C5H4)} Cl2] (M = Ti (20a), Zr (20b)) and [M{CH2CHCH 2(H)Si(η5-C5Me4) 2}Cl2] (M = Ti (21a), Zr (21b), Hf (21c)) were synthesized from the reaction of the lithium ansa-derivatives and the tetrachloride salts of the transition metal. The reactivity of the group 4 metal complexes in hydrosilylation processes has been studied. The reaction of 16b, 17a and 17b with tetravinylsilane gave [Zr{(CH2CH)3SiCH 2CH2(Et)Si(η5-C5H 4)2}Cl2] (22b) and [M{(CH2CH) 3SiCH2CH2(Et)Si(η5-C 5Me4)(η5-C5H4)} Cl2] (M = Ti (23a), Zr (23b)), respectively. The reaction of 17a and 17b with dimethyldivinylsilane yielded the hydrosilylation products [M{(CH 2CH)Me2SiCH2CH2(Et) Si(η5-C5Me4)(η5-C 5H4)}Cl2] (M = Ti (24a), Zr (24b)), respectively. 23b and 24b reacted with the silane reagent HSiEt3 to form, via hydrosilylation, [Zr{(Et3SiCH2CH 2)3SiCH2CH2(Et)Si(η5- C5Me4)(η5-C5H 4)}Cl2] (25b) and [Zr{(Et3SiCH 2CH2)Me2SiCH2CH2(Et) Si(η5-C5Me4)(η5-C 5H4)}Cl2] (26b), respectively. The previously synthesized compounds, [M{CH2CH(Me)Si(η5-C 5Me4)2}Cl2] (M = Ti (27a), Zr (27b)) and [Zr{CH2CHCH2(Me)Si(η5-C 5Me4)2}Cl2] (28b), have also been tested in reactions of hydrosilylation with SiHMeCl2 to give [M{Cl2MeSiCH2CH2(Me)Si(η5- C5Me4)2}Cl2] (M = Ti (29a), Zr (29b)) and [Zr{Cl2MeSiCH2CH2CH 2(Me)Si(η5-C5Me4) 2}Cl2] (30b). All the zirconocene compounds are active to varying degrees as catalysts in the polymerization of ethylene. The molecular structures of 21b and 21c have been determined by single crystal X-ray diffraction studies.

AB - The following ansa-ligand precursors, Et(H)Si(C5H 5)2 (1), Et(H)Si(C5HMe4)Cl (2), Et(H)Si(C5HMe4)(C5H5) (3), Ph(H)Si(C5HMe4)Cl (4), Ph(H)Si(C5HMe 4)(C5H5) (5), Ph(H)Si(C5HMe 4)2 (6), CH2CHCH2(H)Si(C 5HMe4)Cl (7), CH2CHCH2(H)Si(C 5HMe4)(C5H5) (8), CH 2CHCH2(H)Si(C5HMe4)2 (9), and their lithium derivatives, Li2{Et(H)Si(C5H 4)2} (10), Li2{Et(H)Si(C5Me 4)(C5H4)} (11), Li2{Ph(H)Si(C 5Me4)(C5H4)} (12), Li 2{Ph(H)Si(C5Me4)2} (13), Li 2{CH2CHCH2(H)Si(C5Me 4)(C5H4)} (14) and Li2{CH 2CHCH2(H)Si(C5Me4)2} (15) have been prepared. The group 4 metal complexes, [M{Et(H)Si(η5- C5H4)2}Cl2] (M = Ti (16a), Zr (16b), Hf (16c)), [M{Et(H)Si(η5-C5Me4) (η5-C5H4)}Cl2] (M = Ti (17a), Zr (17b), Hf (17c)), [M{Ph(H)Si(η5-C5Me 4)(η5-C5H4)}Cl2] (M = Ti (18a), Zr (18b), Hf (18c)), [M{Ph(H)Si(η5-C 5Me4)2}Cl2] (M = Ti(19a), Zr (19b), Hf (19c)), M{CH2CHCH2(H)Si(η5-C 5Me4)(η5-C5H4)} Cl2] (M = Ti (20a), Zr (20b)) and [M{CH2CHCH 2(H)Si(η5-C5Me4) 2}Cl2] (M = Ti (21a), Zr (21b), Hf (21c)) were synthesized from the reaction of the lithium ansa-derivatives and the tetrachloride salts of the transition metal. The reactivity of the group 4 metal complexes in hydrosilylation processes has been studied. The reaction of 16b, 17a and 17b with tetravinylsilane gave [Zr{(CH2CH)3SiCH 2CH2(Et)Si(η5-C5H 4)2}Cl2] (22b) and [M{(CH2CH) 3SiCH2CH2(Et)Si(η5-C 5Me4)(η5-C5H4)} Cl2] (M = Ti (23a), Zr (23b)), respectively. The reaction of 17a and 17b with dimethyldivinylsilane yielded the hydrosilylation products [M{(CH 2CH)Me2SiCH2CH2(Et) Si(η5-C5Me4)(η5-C 5H4)}Cl2] (M = Ti (24a), Zr (24b)), respectively. 23b and 24b reacted with the silane reagent HSiEt3 to form, via hydrosilylation, [Zr{(Et3SiCH2CH 2)3SiCH2CH2(Et)Si(η5- C5Me4)(η5-C5H 4)}Cl2] (25b) and [Zr{(Et3SiCH 2CH2)Me2SiCH2CH2(Et) Si(η5-C5Me4)(η5-C 5H4)}Cl2] (26b), respectively. The previously synthesized compounds, [M{CH2CH(Me)Si(η5-C 5Me4)2}Cl2] (M = Ti (27a), Zr (27b)) and [Zr{CH2CHCH2(Me)Si(η5-C 5Me4)2}Cl2] (28b), have also been tested in reactions of hydrosilylation with SiHMeCl2 to give [M{Cl2MeSiCH2CH2(Me)Si(η5- C5Me4)2}Cl2] (M = Ti (29a), Zr (29b)) and [Zr{Cl2MeSiCH2CH2CH 2(Me)Si(η5-C5Me4) 2}Cl2] (30b). All the zirconocene compounds are active to varying degrees as catalysts in the polymerization of ethylene. The molecular structures of 21b and 21c have been determined by single crystal X-ray diffraction studies.

KW - Hafnium

KW - Hydrosilylation

KW - Polymerization

KW - Titanium

KW - Zirconium

KW - ansa-Metallocene complexes

UR - http://www.scopus.com/inward/record.url?scp=22844447721&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2005.03.056

DO - 10.1016/j.poly.2005.03.056

M3 - 文章

AN - SCOPUS:22844447721

SN - 0277-5387

VL - 24

SP - 1298

EP - 1313

JO - Polyhedron

JF - Polyhedron

IS - 11

ER -

Synthesis, hydrosilylation reactivity and catalytic properties of group 4 ansa-metallocene complexes

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