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 -