Manganese catalysed dehydrocoupling of silanes and siloxanes with ammonia to prepare oligosilazanes and polysiloxazanes

Gautam K. Mehta; Thao T. Nguyen; Marco Flores; Ryan J. Trovitch

doi:10.1039/d4dt01982b

Manganese catalysed dehydrocoupling of silanes and siloxanes with ammonia to prepare oligosilazanes and polysiloxazanes

Gautam K. Mehta, Thao T. Nguyen, Marco Flores, Ryan J. Trovitch

Molecular Sciences, School of (SMS)

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

Abstract

The halogen-free synthesis of oligosilazanes has been observed upon dehydrocoupling silanes with ammonia at 25 °C using [(^2,6-iPr₂PhBDI)Mn(μ-H)]₂. Extending this methodology to polymethylhydrosiloxanes afforded thermally robust polysiloxazane solids, and the dehydrocoupling of 1,3,5,7-tetramethylcyclotetrasiloxane with ammonia afforded a polysiloxazane having a weight-average molecular weight of 4300 g mol⁻¹. A representative oligosilazane has been applied to a copper surface and found to afford a 20 μm thick coating that resists corrosion after 24 h under water. Addition of ammonia to [(^2,6-iPr₂PhBDI)Mn(μ-H)]₂ allowed for characterization of the catalyst resting state, [(^2,6-iPr₂PhBDI)Mn(μ-NH₂)]₂, which has been found to mediate Si-N dehydrocoupling.

Original language	English (US)
Pages (from-to)	14272-14277
Number of pages	6
Journal	Dalton Transactions
Volume	53
Issue number	34
DOIs	https://doi.org/10.1039/d4dt01982b
State	Published - Jul 27 2024

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Inorganic Chemistry

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title = "Manganese catalysed dehydrocoupling of silanes and siloxanes with ammonia to prepare oligosilazanes and polysiloxazanes",

abstract = "The halogen-free synthesis of oligosilazanes has been observed upon dehydrocoupling silanes with ammonia at 25 °C using [(2,6-iPr2PhBDI)Mn(μ-H)]2. Extending this methodology to polymethylhydrosiloxanes afforded thermally robust polysiloxazane solids, and the dehydrocoupling of 1,3,5,7-tetramethylcyclotetrasiloxane with ammonia afforded a polysiloxazane having a weight-average molecular weight of 4300 g mol−1. A representative oligosilazane has been applied to a copper surface and found to afford a 20 μm thick coating that resists corrosion after 24 h under water. Addition of ammonia to [(2,6-iPr2PhBDI)Mn(μ-H)]2 allowed for characterization of the catalyst resting state, [(2,6-iPr2PhBDI)Mn(μ-NH2)]2, which has been found to mediate Si-N dehydrocoupling.",

author = "Mehta, {Gautam K.} and Nguyen, {Thao T.} and Marco Flores and Trovitch, {Ryan J.}",

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doi = "10.1039/d4dt01982b",

language = "English (US)",

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T1 - Manganese catalysed dehydrocoupling of silanes and siloxanes with ammonia to prepare oligosilazanes and polysiloxazanes

AU - Mehta, Gautam K.

AU - Nguyen, Thao T.

AU - Flores, Marco

AU - Trovitch, Ryan J.

PY - 2024/7/27

Y1 - 2024/7/27

N2 - The halogen-free synthesis of oligosilazanes has been observed upon dehydrocoupling silanes with ammonia at 25 °C using [(2,6-iPr2PhBDI)Mn(μ-H)]2. Extending this methodology to polymethylhydrosiloxanes afforded thermally robust polysiloxazane solids, and the dehydrocoupling of 1,3,5,7-tetramethylcyclotetrasiloxane with ammonia afforded a polysiloxazane having a weight-average molecular weight of 4300 g mol−1. A representative oligosilazane has been applied to a copper surface and found to afford a 20 μm thick coating that resists corrosion after 24 h under water. Addition of ammonia to [(2,6-iPr2PhBDI)Mn(μ-H)]2 allowed for characterization of the catalyst resting state, [(2,6-iPr2PhBDI)Mn(μ-NH2)]2, which has been found to mediate Si-N dehydrocoupling.

AB - The halogen-free synthesis of oligosilazanes has been observed upon dehydrocoupling silanes with ammonia at 25 °C using [(2,6-iPr2PhBDI)Mn(μ-H)]2. Extending this methodology to polymethylhydrosiloxanes afforded thermally robust polysiloxazane solids, and the dehydrocoupling of 1,3,5,7-tetramethylcyclotetrasiloxane with ammonia afforded a polysiloxazane having a weight-average molecular weight of 4300 g mol−1. A representative oligosilazane has been applied to a copper surface and found to afford a 20 μm thick coating that resists corrosion after 24 h under water. Addition of ammonia to [(2,6-iPr2PhBDI)Mn(μ-H)]2 allowed for characterization of the catalyst resting state, [(2,6-iPr2PhBDI)Mn(μ-NH2)]2, which has been found to mediate Si-N dehydrocoupling.

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DO - 10.1039/d4dt01982b

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JO - Dalton Transactions

JF - Dalton Transactions

IS - 34

ER -

Manganese catalysed dehydrocoupling of silanes and siloxanes with ammonia to prepare oligosilazanes and polysiloxazanes

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