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Issue 8, 2018
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New reactivity at the silicon bridge in sila[1]ferrocenophanes

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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)2Si(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)2SiMe2] (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(C5H4SiMe2Cl){C5H4Au(PMe3)}] (14). This represents the first example of ring-opening addition of a metallocenophane with a reagent possessing a transition metal–halogen bond.

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

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Publication details

The article was received on 06 Dec 2017, accepted on 22 Jan 2018 and first published on 23 Jan 2018


Article type: Paper
DOI: 10.1039/C7DT04593J
Citation: Dalton Trans., 2018,47, 2759-2768
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    New reactivity at the silicon bridge in sila[1]ferrocenophanes

    R. A. Musgrave, R. L. N. Hailes, A. Schäfer, A. D. Russell, P. J. Gates and I. Manners, Dalton Trans., 2018, 47, 2759
    DOI: 10.1039/C7DT04593J

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