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

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)155-162
Number of pages8
JournalJournal of Organometallic Chemistry
Volume473
Issue number1-2
DOIs
Publication statusPublished - 1994 Jun 28

Fingerprint

dihydrides
Tungsten
Methacrylates
Alkenes
alkenes
Olefins
Derivatives
preparation
Molybdenum
probes
Photolysis
tungsten
Benzene
Reaction rates
borohydrides
dichlorides
Sodium
X-Rays
X rays
Crystals

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

Cite this

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; Kobayashi, Kimiko; Shimizu, Isao; Yamamoto, Yasuhiro; Wakatsuki, Yasuo.

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

Research output: Contribution to journalArticle

Mise, Takaya ; Maeda, Mami ; Nakajima, Takayuki ; Kobayashi, Kimiko ; Shimizu, Isao ; Yamamoto, Yasuhiro ; Wakatsuki, Yasuo. / 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. In: Journal of Organometallic Chemistry. 1994 ; Vol. 473, No. 1-2. pp. 155-162.
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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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T1 - 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

AU - Mise, Takaya

AU - Maeda, Mami

AU - Nakajima, Takayuki

AU - Kobayashi, Kimiko

AU - Shimizu, Isao

AU - Yamamoto, Yasuhiro

AU - Wakatsuki, Yasuo

PY - 1994/6/28

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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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