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 | |
| Publication status | Published - 1994 Jun 28 |
Fingerprint
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 journal › Article
}
TY - JOUR
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
Y1 - 1994/6/28
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).
KW - Bridging ligand
KW - Metallocenes
KW - Methyl methacrylate
KW - Molybdenum
KW - Tungsten
UR - http://www.scopus.com/inward/record.url?scp=0000309489&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0000309489&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(94)80116-9
DO - 10.1016/0022-328X(94)80116-9
M3 - Article
AN - SCOPUS:0000309489
VL - 473
SP - 155
EP - 162
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1-2
ER -