Ferrocene-Containing Polycarbosilazanes via the Alkaline-Earth-Catalyzed Dehydrocoupling of Silanes and Amines

Louis J. Morris; George R. Whittell; Jean Charles Eloi; Mary F. Mahon; Frank Marken; Ian Manners; Michael S. Hill

doi:10.1021/acs.organomet.9b00444

Ferrocene-Containing Polycarbosilazanes via the Alkaline-Earth-Catalyzed Dehydrocoupling of Silanes and Amines

Louis J. Morris, George R. Whittell, Jean Charles Eloi, Mary F. Mahon, Frank Marken, Ian Manners, Michael S. Hill

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Abstract

We report the use of the alkaline-earth (Ae) metal-catalyzed dehydrocoupling of silanes and amines for the synthesis of ferrocene-containing polycarbosilazanes. The barium complex [Ba(N(SiMe ₃) ₂) ₂·(THF) ₂] catalyzed the dehydrocoupling of the hydrosilane FeCp(CpSiPhH ₂) (1) with 1,4-(H ₂NCH ₂) ₂C ₆H ₄ under mild conditions to give a polycarbosilazane with pendant ferrocene groups. The polymer could be readily cross-linked by the addition of phenylsilane to the unquenched reaction mixture. Well-defined polycarbosilazanes with ferrocene in the main chain were also obtained from the dehydrocoupling of hydrosilanes Fe(Cp(SiPhH ₂)) ₂ (3) and Fe(Cp(SiMe ₂H)) ₂ (IX) with 1,4-(H(Me)NCH ₂) ₂C ₆H ₄ and 1,4-(H ₂NCH ₂) ₂C ₆H ₄, respectively. Crystalline monomeric analogues, FeCp(Cp(SiPh(NHBn) ₂)) (2, Bn = CH ₂(C ₆H ₅)), and Fe(Cp(SiPh(NHBn) ₂)) ₂ (4), were also obtained via the dehydrocoupling benzylamine with 1 and 3, respectively. The barium-catalyzed dehydrocoupling of diaminoferrocene with Ph ₂SiH ₂ or Ph(Rc)SiH ₂ (6, Rc = (C ₅H ₄)Ru(C ₅H ₅)) did not result in polymer, but instead in the formation of the silazane-bridged ansa-[3]ferrocenophanes (Fe(ν-C ₅H ₄NH) ₂SiPh ₂) (5) and (Fe(ν-C ₅H ₄NH) ₂SiPh(Rc)) (7), respectively. Both polymeric and molecular products were electrochemically investigated, and the polymers proved to be promising precursors to magnetic iron-containing ceramics in yields of up to 64%.

Original language	English
Pages (from-to)	3629-3648
Number of pages	20
Journal	Organometallics
Volume	38
Issue number	19
Early online date	24 Sept 2019
DOIs	https://doi.org/10.1021/acs.organomet.9b00444
Publication status	Published - 14 Oct 2019

Funding

We acknowledge financial support from the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1) and Dr. John Lowe (University of Bath) for his assistance with DOSY experiments. I.M. thanks the University of Bristol for support and the Canadian Government for a C150 Research Chair.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.organomet.9b00444
Accepted author manuscript, 2.36 MBLicence: Unspecified

Cite this

@article{2bd22032840440fea83b0942c685621f,

title = "Ferrocene-Containing Polycarbosilazanes via the Alkaline-Earth-Catalyzed Dehydrocoupling of Silanes and Amines",

abstract = "We report the use of the alkaline-earth (Ae) metal-catalyzed dehydrocoupling of silanes and amines for the synthesis of ferrocene-containing polycarbosilazanes. The barium complex [Ba(N(SiMe 3) 2) 2·(THF) 2] catalyzed the dehydrocoupling of the hydrosilane FeCp(CpSiPhH 2) (1) with 1,4-(H 2NCH 2) 2C 6H 4 under mild conditions to give a polycarbosilazane with pendant ferrocene groups. The polymer could be readily cross-linked by the addition of phenylsilane to the unquenched reaction mixture. Well-defined polycarbosilazanes with ferrocene in the main chain were also obtained from the dehydrocoupling of hydrosilanes Fe(Cp(SiPhH 2)) 2 (3) and Fe(Cp(SiMe 2H)) 2 (IX) with 1,4-(H(Me)NCH 2) 2C 6H 4 and 1,4-(H 2NCH 2) 2C 6H 4, respectively. Crystalline monomeric analogues, FeCp(Cp(SiPh(NHBn) 2)) (2, Bn = CH 2(C 6H 5)), and Fe(Cp(SiPh(NHBn) 2)) 2 (4), were also obtained via the dehydrocoupling benzylamine with 1 and 3, respectively. The barium-catalyzed dehydrocoupling of diaminoferrocene with Ph 2SiH 2 or Ph(Rc)SiH 2 (6, Rc = (C 5H 4)Ru(C 5H 5)) did not result in polymer, but instead in the formation of the silazane-bridged ansa-[3]ferrocenophanes (Fe(ν-C 5H 4NH) 2SiPh 2) (5) and (Fe(ν-C 5H 4NH) 2SiPh(Rc)) (7), respectively. Both polymeric and molecular products were electrochemically investigated, and the polymers proved to be promising precursors to magnetic iron-containing ceramics in yields of up to 64%. ",

author = "Morris, {Louis J.} and Whittell, {George R.} and Eloi, {Jean Charles} and Mahon, {Mary F.} and Frank Marken and Ian Manners and Hill, {Michael S.}",

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AU - Morris, Louis J.

AU - Whittell, George R.

AU - Eloi, Jean Charles

AU - Mahon, Mary F.

AU - Marken, Frank

AU - Manners, Ian

AU - Hill, Michael S.

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N2 - We report the use of the alkaline-earth (Ae) metal-catalyzed dehydrocoupling of silanes and amines for the synthesis of ferrocene-containing polycarbosilazanes. The barium complex [Ba(N(SiMe 3) 2) 2·(THF) 2] catalyzed the dehydrocoupling of the hydrosilane FeCp(CpSiPhH 2) (1) with 1,4-(H 2NCH 2) 2C 6H 4 under mild conditions to give a polycarbosilazane with pendant ferrocene groups. The polymer could be readily cross-linked by the addition of phenylsilane to the unquenched reaction mixture. Well-defined polycarbosilazanes with ferrocene in the main chain were also obtained from the dehydrocoupling of hydrosilanes Fe(Cp(SiPhH 2)) 2 (3) and Fe(Cp(SiMe 2H)) 2 (IX) with 1,4-(H(Me)NCH 2) 2C 6H 4 and 1,4-(H 2NCH 2) 2C 6H 4, respectively. Crystalline monomeric analogues, FeCp(Cp(SiPh(NHBn) 2)) (2, Bn = CH 2(C 6H 5)), and Fe(Cp(SiPh(NHBn) 2)) 2 (4), were also obtained via the dehydrocoupling benzylamine with 1 and 3, respectively. The barium-catalyzed dehydrocoupling of diaminoferrocene with Ph 2SiH 2 or Ph(Rc)SiH 2 (6, Rc = (C 5H 4)Ru(C 5H 5)) did not result in polymer, but instead in the formation of the silazane-bridged ansa-[3]ferrocenophanes (Fe(ν-C 5H 4NH) 2SiPh 2) (5) and (Fe(ν-C 5H 4NH) 2SiPh(Rc)) (7), respectively. Both polymeric and molecular products were electrochemically investigated, and the polymers proved to be promising precursors to magnetic iron-containing ceramics in yields of up to 64%.

AB - We report the use of the alkaline-earth (Ae) metal-catalyzed dehydrocoupling of silanes and amines for the synthesis of ferrocene-containing polycarbosilazanes. The barium complex [Ba(N(SiMe 3) 2) 2·(THF) 2] catalyzed the dehydrocoupling of the hydrosilane FeCp(CpSiPhH 2) (1) with 1,4-(H 2NCH 2) 2C 6H 4 under mild conditions to give a polycarbosilazane with pendant ferrocene groups. The polymer could be readily cross-linked by the addition of phenylsilane to the unquenched reaction mixture. Well-defined polycarbosilazanes with ferrocene in the main chain were also obtained from the dehydrocoupling of hydrosilanes Fe(Cp(SiPhH 2)) 2 (3) and Fe(Cp(SiMe 2H)) 2 (IX) with 1,4-(H(Me)NCH 2) 2C 6H 4 and 1,4-(H 2NCH 2) 2C 6H 4, respectively. Crystalline monomeric analogues, FeCp(Cp(SiPh(NHBn) 2)) (2, Bn = CH 2(C 6H 5)), and Fe(Cp(SiPh(NHBn) 2)) 2 (4), were also obtained via the dehydrocoupling benzylamine with 1 and 3, respectively. The barium-catalyzed dehydrocoupling of diaminoferrocene with Ph 2SiH 2 or Ph(Rc)SiH 2 (6, Rc = (C 5H 4)Ru(C 5H 5)) did not result in polymer, but instead in the formation of the silazane-bridged ansa-[3]ferrocenophanes (Fe(ν-C 5H 4NH) 2SiPh 2) (5) and (Fe(ν-C 5H 4NH) 2SiPh(Rc)) (7), respectively. Both polymeric and molecular products were electrochemically investigated, and the polymers proved to be promising precursors to magnetic iron-containing ceramics in yields of up to 64%.

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Ferrocene-Containing Polycarbosilazanes via the Alkaline-Earth-Catalyzed Dehydrocoupling of Silanes and Amines

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Ferrocene-Containing Polycarbosilazanes via the Alkaline-Earth-Catalyzed Dehydrocoupling of Silanes and Amines

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Equipment

Avance NEO 500 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (1South)

Differential Scanning Calorimeter (DSC)

Dual source (Cu and Mo) Single Crystal Diffractometer (SuperNova)

Cite this