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

*この研究の対応する著者

研究成果: Article › 査読

12 被引用数 (Scopus)

抄録

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).

本文言語English
ページ（範囲）155-162
ページ数8
ジャーナルJournal of Organometallic Chemistry
巻473
号1-2
DOI
出版ステータスPublished - 1994 6月 28

ASJC Scopus subject areas

  • 生化学
  • 化学工学（その他）
  • 無機化学
  • 有機化学
  • 物理化学および理論化学
  • 材料科学（その他）
  • 材料化学

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