Syntheses of transition metal methoxysiloxides

Casseday P. Richers; Jeffery A. Bertke; Thomas B. Rauchfuss

doi:10.1039/c6dt04205h

Syntheses of transition metal methoxysiloxides

Casseday P. Richers
, Jeffery A. Bertke
, Thomas B. Rauchfuss

Chemistry

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

Abstract

The paper describes three methods for the preparation of methoxysiloxide complexes, a rare class of complexes of relevance to room temperature vulcanization (RTV) of polysiloxanes. The salt metathesis reaction involves the use of the recently described reagent NaOSi(OMe)₂Me with various metal chlorides to give Cp∗₂Ti[OSi(OMe)₂Me](OMe), (^Me,MeN₂N)NiOSi(OMe)₂Me, (IPr)CuOSi(OMe)₂Me, and (triphos)CoOSi(OMe)₂Me (Cp∗ = C₅Me₅, triphos = Me(CH₂PPh₂)₃). Several attempted reactions gave methoxide complexes instead, a pathway that is attributed to the intermediacy of κ²-OSi(OMe)₂Me species. The diol Cp∗₂Zr(OH)₂ reacts with excess (MeO)₃SiMe to give Cp∗₂Zr[OSi(OMe)₂Me]₂. In contrast the less nucleophilic Cp∗₂Ti(OH)₂ was unreactive. The third route to methoxysiloxide complexes involves the reaction of Cp∗₂M(O)(py) with (MeO)₃SiMe to give Cp∗₂M[OSi(OMe)₂Me](OMe) in nearly quantitative yield (M = Ti, Zr). The structures of Cp∗₂Ti[OSi(OMe)₂Me](OMe), Cp∗₂Zr[OSi(OMe)₂Me](OMe), (IPr)CuOSi(OMe)₂Me, and (triphos)CoOSi(OMe)₂Me were confirmed by single crystal X-ray diffraction.

Original language	English (US)
Pages (from-to)	8756-8762
Number of pages	7
Journal	Dalton Transactions
Volume	46
Issue number	27
DOIs	https://doi.org/10.1039/c6dt04205h
State	Published - 2017

ASJC Scopus subject areas

Inorganic Chemistry

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10.1039/c6dt04205h

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title = "Syntheses of transition metal methoxysiloxides",

abstract = "The paper describes three methods for the preparation of methoxysiloxide complexes, a rare class of complexes of relevance to room temperature vulcanization (RTV) of polysiloxanes. The salt metathesis reaction involves the use of the recently described reagent NaOSi(OMe)2Me with various metal chlorides to give Cp∗2Ti[OSi(OMe)2Me](OMe), (Me,MeN2N)NiOSi(OMe)2Me, (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me (Cp∗ = C5Me5, triphos = Me(CH2PPh2)3). Several attempted reactions gave methoxide complexes instead, a pathway that is attributed to the intermediacy of κ2-OSi(OMe)2Me species. The diol Cp∗2Zr(OH)2 reacts with excess (MeO)3SiMe to give Cp∗2Zr[OSi(OMe)2Me]2. In contrast the less nucleophilic Cp∗2Ti(OH)2 was unreactive. The third route to methoxysiloxide complexes involves the reaction of Cp∗2M(O)(py) with (MeO)3SiMe to give Cp∗2M[OSi(OMe)2Me](OMe) in nearly quantitative yield (M = Ti, Zr). The structures of Cp∗2Ti[OSi(OMe)2Me](OMe), Cp∗2Zr[OSi(OMe)2Me](OMe), (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me were confirmed by single crystal X-ray diffraction.",

author = "Richers, \{Casseday P.\} and Bertke, \{Jeffery A.\} and Rauchfuss, \{Thomas B.\}",

note = "This research was supported by NSF CHE 15-66023. Dow Corning Corporation sponsored initial stages of this project. We thank Drs Loren Durfee, Shuanbing Han, and Matthew Olsen for advice.",

year = "2017",

doi = "10.1039/c6dt04205h",

language = "English (US)",

volume = "46",

pages = "8756--8762",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Syntheses of transition metal methoxysiloxides

AU - Richers, Casseday P.

AU - Bertke, Jeffery A.

AU - Rauchfuss, Thomas B.

N1 - This research was supported by NSF CHE 15-66023. Dow Corning Corporation sponsored initial stages of this project. We thank Drs Loren Durfee, Shuanbing Han, and Matthew Olsen for advice.

PY - 2017

Y1 - 2017

N2 - The paper describes three methods for the preparation of methoxysiloxide complexes, a rare class of complexes of relevance to room temperature vulcanization (RTV) of polysiloxanes. The salt metathesis reaction involves the use of the recently described reagent NaOSi(OMe)2Me with various metal chlorides to give Cp∗2Ti[OSi(OMe)2Me](OMe), (Me,MeN2N)NiOSi(OMe)2Me, (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me (Cp∗ = C5Me5, triphos = Me(CH2PPh2)3). Several attempted reactions gave methoxide complexes instead, a pathway that is attributed to the intermediacy of κ2-OSi(OMe)2Me species. The diol Cp∗2Zr(OH)2 reacts with excess (MeO)3SiMe to give Cp∗2Zr[OSi(OMe)2Me]2. In contrast the less nucleophilic Cp∗2Ti(OH)2 was unreactive. The third route to methoxysiloxide complexes involves the reaction of Cp∗2M(O)(py) with (MeO)3SiMe to give Cp∗2M[OSi(OMe)2Me](OMe) in nearly quantitative yield (M = Ti, Zr). The structures of Cp∗2Ti[OSi(OMe)2Me](OMe), Cp∗2Zr[OSi(OMe)2Me](OMe), (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me were confirmed by single crystal X-ray diffraction.

AB - The paper describes three methods for the preparation of methoxysiloxide complexes, a rare class of complexes of relevance to room temperature vulcanization (RTV) of polysiloxanes. The salt metathesis reaction involves the use of the recently described reagent NaOSi(OMe)2Me with various metal chlorides to give Cp∗2Ti[OSi(OMe)2Me](OMe), (Me,MeN2N)NiOSi(OMe)2Me, (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me (Cp∗ = C5Me5, triphos = Me(CH2PPh2)3). Several attempted reactions gave methoxide complexes instead, a pathway that is attributed to the intermediacy of κ2-OSi(OMe)2Me species. The diol Cp∗2Zr(OH)2 reacts with excess (MeO)3SiMe to give Cp∗2Zr[OSi(OMe)2Me]2. In contrast the less nucleophilic Cp∗2Ti(OH)2 was unreactive. The third route to methoxysiloxide complexes involves the reaction of Cp∗2M(O)(py) with (MeO)3SiMe to give Cp∗2M[OSi(OMe)2Me](OMe) in nearly quantitative yield (M = Ti, Zr). The structures of Cp∗2Ti[OSi(OMe)2Me](OMe), Cp∗2Zr[OSi(OMe)2Me](OMe), (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me were confirmed by single crystal X-ray diffraction.

UR - https://www.scopus.com/pages/publications/85023763869

UR - https://www.scopus.com/pages/publications/85023763869#tab=citedBy

U2 - 10.1039/c6dt04205h

DO - 10.1039/c6dt04205h

M3 - Article

C2 - 28138664

AN - SCOPUS:85023763869

SN - 1477-9226

VL - 46

SP - 8756

EP - 8762

JO - Dalton Transactions

JF - Dalton Transactions

IS - 27

ER -

Syntheses of transition metal methoxysiloxides

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