Electron-rich siloxane-platinum complexes - Synthesis, structures, and reactivity

Roman Goikhman; Tanya Karakuz; Linda J.W. Shimon; Gregory Leitus; David Milstein

doi:10.1139/v05-041

Electron-rich siloxane-platinum complexes - Synthesis, structures, and reactivity

Roman Goikhman, Tanya Karakuz, Linda J.W. Shimon, Gregory Leitus, David Milstein

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

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	https://doi.org/10.1139/v05-041
Publication status	Published - Jun 1 2005

Keywords

Cyclosiloxane
Lewis base
Metallacycle
Oxidative addition
Platinum silyl

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Organic Chemistry

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title = "Electron-rich siloxane-platinum complexes - Synthesis, structures, and reactivity",

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.",

keywords = "Cyclosiloxane, Lewis base, Metallacycle, Oxidative addition, Platinum silyl",

author = "Roman Goikhman and Tanya Karakuz and Shimon, {Linda J.W.} and Gregory Leitus and David Milstein",

year = "2005",

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doi = "10.1139/v05-041",

language = "English",

volume = "83",

pages = "786--792",

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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 - 2005/6/1

Y1 - 2005/6/1

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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Electron-rich siloxane-platinum complexes - Synthesis, structures, and reactivity

Abstract

Keywords

ASJC Scopus subject areas

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