Preparation and structure of the first ansa-molybdenocene and tungstenocene derivatives. Reaction of [O(SiMe2C5H4)2]MoH2 with methyl methacrylate to probe the olefin attacking site

Takaya Mise; Mami Maeda; Takayuki Nakajima; Kimiko Kobayashi; Isao Shimizu; Yasuhiro Yamamoto; Yasuo Wakatsuki

doi:10.1016/0022-328X(94)80116-9

Preparation and structure of the first ansa-molybdenocene and tungstenocene derivatives. Reaction of [O(SiMe₂C₅H₄)₂]MoH₂ with methyl methacrylate to probe the olefin attacking site

Takaya Mise^*, Mami Maeda, Takayuki Nakajima, Kimiko Kobayashi, Isao Shimizu, Yasuhiro Yamamoto, Yasuo Wakatsuki

^*Corresponding author for this work

Waseda University

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

12 Citations (Scopus)

Abstract

Bridged-bis(cyclopentadienyl) molybdenum and tungsten dihydrides and their derivatives have been synthesized for the first time. [(1,1,3,3-Tetramethyldisiloxane-1,3-diyl)bis(η⁵-cyclopentadienyl)lmolybdenum dihydride (1a) and tungsten dihydride (1b) were prepared by sodium borohydride reduction of [O(SiMe₂C₅H₄)₂]MCl₂ (2a: M Mo, 2b: M W) which was obtained by the reaction of disodium 1,1,3,3-tetramethyl-1,3-bis(cyclopentadienyl)disiloxane with MCl₄(thf)₂ (M Mo, W). The dichlorides 2 reacted with ZnMe₂ and NaSEt to afford [O(SiMe₂C₅H₄)₂]MMe₂ (3a: M Mo, 3b: M W) and [O(SiMe₂C₅H₄)₂]M(SEt)₂ (4a: M Mo, 4b: M W), respectively. Photolysis of 1b in benzene gave [O(SiMe₂C₅H₄)₂]WH(C₆H₅) (5b). An X-ray crystal analysis of 3a has proved that the bridging chain blocks one of the side positions of the complex, the siloxy unit being present at one side of the MeMoMe bisector. Consistent with side position attack by olefins, the reaction rate of 1a with methyl methacrylate was found to be nearly one half that of the parent Cp₂MoH₂ (6a).

Original language	English
Pages (from-to)	155-162
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	473
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(94)80116-9
Publication status	Published - 1994 Jun 28

Keywords

Bridging ligand
Metallocenes
Methyl methacrylate
Molybdenum
Tungsten

ASJC Scopus subject areas

Biochemistry
Chemical Engineering (miscellaneous)
Inorganic Chemistry
Organic Chemistry
Physical and Theoretical Chemistry
Materials Science (miscellaneous)
Materials Chemistry

Access to Document

10.1016/0022-328X(94)80116-9

Cite this

Mise, T., Maeda, M., Nakajima, T., Kobayashi, K., Shimizu, I., Yamamoto, Y., & Wakatsuki, Y. (1994). Preparation and structure of the first ansa-molybdenocene and tungstenocene derivatives. Reaction of [O(SiMe₂C₅H₄)₂]MoH₂ with methyl methacrylate to probe the olefin attacking site. Journal of Organometallic Chemistry, 473(1-2), 155-162. https://doi.org/10.1016/0022-328X(94)80116-9

Preparation and structure of the first ansa-molybdenocene and tungstenocene derivatives. Reaction of [O(SiMe₂C₅H₄)₂]MoH₂ with methyl methacrylate to probe the olefin attacking site. / Mise, Takaya; Maeda, Mami; Nakajima, Takayuki et al.

In: Journal of Organometallic Chemistry, Vol. 473, No. 1-2, 28.06.1994, p. 155-162.

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

Mise, T, Maeda, M, Nakajima, T, Kobayashi, K, Shimizu, I, Yamamoto, Y & Wakatsuki, Y 1994, 'Preparation and structure of the first ansa-molybdenocene and tungstenocene derivatives. Reaction of [O(SiMe₂C₅H₄)₂]MoH₂ with methyl methacrylate to probe the olefin attacking site', Journal of Organometallic Chemistry, vol. 473, no. 1-2, pp. 155-162. https://doi.org/10.1016/0022-328X(94)80116-9

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title = "Preparation and structure of the first ansa-molybdenocene and tungstenocene derivatives. Reaction of [O(SiMe2C5H4)2]MoH2 with methyl methacrylate to probe the olefin attacking site",

abstract = "Bridged-bis(cyclopentadienyl) molybdenum and tungsten dihydrides and their derivatives have been synthesized for the first time. [(1,1,3,3-Tetramethyldisiloxane-1,3-diyl)bis(η5-cyclopentadienyl)lmolybdenum dihydride (1a) and tungsten dihydride (1b) were prepared by sodium borohydride reduction of [O(SiMe2C5H4)2]MCl2 (2a: M Mo, 2b: M W) which was obtained by the reaction of disodium 1,1,3,3-tetramethyl-1,3-bis(cyclopentadienyl)disiloxane with MCl4(thf)2 (M Mo, W). The dichlorides 2 reacted with ZnMe2 and NaSEt to afford [O(SiMe2C5H4)2]MMe2 (3a: M Mo, 3b: M W) and [O(SiMe2C5H4)2]M(SEt)2 (4a: M Mo, 4b: M W), respectively. Photolysis of 1b in benzene gave [O(SiMe2C5H4)2]WH(C6H5) (5b). An X-ray crystal analysis of 3a has proved that the bridging chain blocks one of the side positions of the complex, the siloxy unit being present at one side of the MeMoMe bisector. Consistent with side position attack by olefins, the reaction rate of 1a with methyl methacrylate was found to be nearly one half that of the parent Cp2MoH2 (6a).",

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AU - Nakajima, Takayuki

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AU - Shimizu, Isao

AU - Yamamoto, Yasuhiro

AU - Wakatsuki, Yasuo

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N2 - Bridged-bis(cyclopentadienyl) molybdenum and tungsten dihydrides and their derivatives have been synthesized for the first time. [(1,1,3,3-Tetramethyldisiloxane-1,3-diyl)bis(η5-cyclopentadienyl)lmolybdenum dihydride (1a) and tungsten dihydride (1b) were prepared by sodium borohydride reduction of [O(SiMe2C5H4)2]MCl2 (2a: M Mo, 2b: M W) which was obtained by the reaction of disodium 1,1,3,3-tetramethyl-1,3-bis(cyclopentadienyl)disiloxane with MCl4(thf)2 (M Mo, W). The dichlorides 2 reacted with ZnMe2 and NaSEt to afford [O(SiMe2C5H4)2]MMe2 (3a: M Mo, 3b: M W) and [O(SiMe2C5H4)2]M(SEt)2 (4a: M Mo, 4b: M W), respectively. Photolysis of 1b in benzene gave [O(SiMe2C5H4)2]WH(C6H5) (5b). An X-ray crystal analysis of 3a has proved that the bridging chain blocks one of the side positions of the complex, the siloxy unit being present at one side of the MeMoMe bisector. Consistent with side position attack by olefins, the reaction rate of 1a with methyl methacrylate was found to be nearly one half that of the parent Cp2MoH2 (6a).

AB - Bridged-bis(cyclopentadienyl) molybdenum and tungsten dihydrides and their derivatives have been synthesized for the first time. [(1,1,3,3-Tetramethyldisiloxane-1,3-diyl)bis(η5-cyclopentadienyl)lmolybdenum dihydride (1a) and tungsten dihydride (1b) were prepared by sodium borohydride reduction of [O(SiMe2C5H4)2]MCl2 (2a: M Mo, 2b: M W) which was obtained by the reaction of disodium 1,1,3,3-tetramethyl-1,3-bis(cyclopentadienyl)disiloxane with MCl4(thf)2 (M Mo, W). The dichlorides 2 reacted with ZnMe2 and NaSEt to afford [O(SiMe2C5H4)2]MMe2 (3a: M Mo, 3b: M W) and [O(SiMe2C5H4)2]M(SEt)2 (4a: M Mo, 4b: M W), respectively. Photolysis of 1b in benzene gave [O(SiMe2C5H4)2]WH(C6H5) (5b). An X-ray crystal analysis of 3a has proved that the bridging chain blocks one of the side positions of the complex, the siloxy unit being present at one side of the MeMoMe bisector. Consistent with side position attack by olefins, the reaction rate of 1a with methyl methacrylate was found to be nearly one half that of the parent Cp2MoH2 (6a).

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