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

研究成果: Article

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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).

元の言語English
ページ(範囲)155-162
ページ数8
ジャーナルJournal of Organometallic Chemistry
473
発行部数1-2
DOI
出版物ステータスPublished - 1994 6 28

ASJC Scopus subject areas

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

フィンガープリント Preparation and structure of the first ansa-molybdenocene and tungstenocene derivatives. Reaction of [O(SiMe<sub>2</sub>C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>]MoH<sub>2</sub> with methyl methacrylate to probe the olefin attacking site' の研究トピックを掘り下げます。これらはともに一意のフィンガープリントを構成します。

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