Abstract
New platinasiloxanes were synthesized and their reactivity was studied. Oxidative addition of (HSiMe2)2O to Pt(PEt 3)3 led to dehydrogenation and quantitative formation of the four-membered platinacyclosiloxane [(PEt3)2Pt- ((SiMe2)2O)] which was characterized by X-ray diffraction. This complex was stable towards non-polar substrates and aerobic conditions, but reacted readily with electrophiles and Lewis acids. Reaction with MeI resulted in ring opening, while MeOTf gave an oxonium complex, with retention of the platinacycle structure. A complex resulting from BF3 coordination to the ring oxygen atom was also obtained. An unprecedented open-chain diplatinasiloxane containing the Pt-Si-O-Si-O-Si-Pt fragment was formed by oxidative addition of H-SiMe2-O-SiMe2-O- SiMe2-H to Pt(PEt3)3 and it was characterized by X-ray diffraction.
| Original language | English |
|---|---|
| Pages (from-to) | 786-792 |
| Number of pages | 7 |
| Journal | Canadian Journal of Chemistry |
| Volume | 83 |
| Issue number | 6-7 |
| DOIs | |
| Publication status | Published - Jun 2005 |
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Keywords
- Cyclosiloxane
- Lewis base
- Metallacycle
- Oxidative addition
- Platinum silyl
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Electron-rich siloxane-platinum complexes - Synthesis, structures, and reactivity. / Goikhman, Roman; Karakuz, Tanya; Shimon, Linda J W; Leitus, Gregory; Milstein, David.
In: Canadian Journal of Chemistry, Vol. 83, No. 6-7, 06.2005, p. 786-792.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Electron-rich siloxane-platinum complexes - Synthesis, structures, and reactivity
AU - Goikhman, Roman
AU - Karakuz, Tanya
AU - Shimon, Linda J W
AU - Leitus, Gregory
AU - Milstein, David
PY - 2005/6
Y1 - 2005/6
N2 - New platinasiloxanes were synthesized and their reactivity was studied. Oxidative addition of (HSiMe2)2O to Pt(PEt 3)3 led to dehydrogenation and quantitative formation of the four-membered platinacyclosiloxane [(PEt3)2Pt- ((SiMe2)2O)] which was characterized by X-ray diffraction. This complex was stable towards non-polar substrates and aerobic conditions, but reacted readily with electrophiles and Lewis acids. Reaction with MeI resulted in ring opening, while MeOTf gave an oxonium complex, with retention of the platinacycle structure. A complex resulting from BF3 coordination to the ring oxygen atom was also obtained. An unprecedented open-chain diplatinasiloxane containing the Pt-Si-O-Si-O-Si-Pt fragment was formed by oxidative addition of H-SiMe2-O-SiMe2-O- SiMe2-H to Pt(PEt3)3 and it was characterized by X-ray diffraction.
AB - New platinasiloxanes were synthesized and their reactivity was studied. Oxidative addition of (HSiMe2)2O to Pt(PEt 3)3 led to dehydrogenation and quantitative formation of the four-membered platinacyclosiloxane [(PEt3)2Pt- ((SiMe2)2O)] which was characterized by X-ray diffraction. This complex was stable towards non-polar substrates and aerobic conditions, but reacted readily with electrophiles and Lewis acids. Reaction with MeI resulted in ring opening, while MeOTf gave an oxonium complex, with retention of the platinacycle structure. A complex resulting from BF3 coordination to the ring oxygen atom was also obtained. An unprecedented open-chain diplatinasiloxane containing the Pt-Si-O-Si-O-Si-Pt fragment was formed by oxidative addition of H-SiMe2-O-SiMe2-O- SiMe2-H to Pt(PEt3)3 and it was characterized by X-ray diffraction.
KW - Cyclosiloxane
KW - Lewis base
KW - Metallacycle
KW - Oxidative addition
KW - Platinum silyl
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U2 - 10.1139/v05-041
DO - 10.1139/v05-041
M3 - Article
VL - 83
SP - 786
EP - 792
JO - Canadian Journal of Chemistry
JF - Canadian Journal of Chemistry
SN - 0008-4042
IS - 6-7
ER -