New reactivity at the silicon bridge in sila[1]ferrocenophanes

Rebecca Musgrave, Rebekah Hailes, Andre Schafer, Andrew Russell, Paul Gates, Ian Manners

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Abstract

We describe two new types of reactivity involving silicon-bridged [1]ferrocenophanes. In an attempt to form a [1]ferrocenophane with a bridging silyl cation, the reaction of sila[1]ferrocenophane [Fe(η-C5H4)Si(H)TMP] (12) (TMP = 2,2,6,6-tetramethylpiperidyl) towards the hydride-abstraction reagent trityl tetrakis(pentafluorophenyl)borate ([CPh3][B(C6F5)4]) was explored. This yielded the unusual dinuclear species [Fe(η-C5H4)2Si(TMP•H)(η-C5H3)Fe(η-C5H4)Si(H)TMP][B(C6F5)4] [13][B(C6F5)4] in low yield. The formation of [13]+
is proposed to involve abstraction of hydride from the silicon bridge in 12 with subsequent C–H bond cleavage of a cyclopentadienyl group by the resulting electrophilic transient silyl cation intermediate. We also explored the reaction of dimethylsila[1]ferrocenophane [Fe(η-C5H4)SiMe2] (1) with the Au(I) species AuCl(PMe3). This was found to result in addition of the Au–Cl bond across the Cpipso–Si bond. to yield
the ring-opened species [1′-(chlorodimethylsilyl)-ferrocenyl](trimethylphosphine)gold(I), [Fe(C5H4Si(Me2Cl)(C5H4Au(PMe3)]
(14). This represents the first example of ring-opening addition of a metallocenophane with a reagent possessing a
transition metal-halogen bond.
Original languageEnglish
Pages (from-to)2759-2768
Number of pages10
JournalDalton Transactions
Volume47
Issue number8
Early online date23 Jan 2018
DOIs
Publication statusPublished - 28 Jan 2018

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    Musgrave, R., Hailes, R., Schafer, A., Russell, A., Gates, P., & Manners, I. (2018). New reactivity at the silicon bridge in sila[1]ferrocenophanes. Dalton Transactions, 47(8), 2759-2768. https://doi.org/10.1039/c7dt04593j