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

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

doi:10.1039/c7dt04593j

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 language	English
Pages (from-to)	2759-2768
Number of pages	10
Journal	Dalton Transactions
Volume	47
Issue number	8
Early online date	23 Jan 2018
DOIs	https://doi.org/10.1039/c7dt04593j
Publication status	Published - 28 Jan 2018

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@article{9e6d6454279741d2a75fed90363b5bed,

title = "New reactivity at the silicon bridge in sila[1]ferrocenophanes",

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 yieldthe 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 atransition metal-halogen bond. ",

author = "Rebecca Musgrave and Rebekah Hailes and Andre Schafer and Andrew Russell and Paul Gates and Ian Manners",

year = "2018",

month = jan,

day = "28",

doi = "10.1039/c7dt04593j",

language = "English",

volume = "47",

pages = "2759--2768",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "8",

}

TY - JOUR

T1 - New reactivity at the silicon bridge in sila[1]ferrocenophanes

AU - Musgrave, Rebecca

AU - Hailes, Rebekah

AU - Schafer, Andre

AU - Russell, Andrew

AU - Gates, Paul

AU - Manners, Ian

PY - 2018/1/28

Y1 - 2018/1/28

N2 - 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 yieldthe 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 atransition metal-halogen bond.

AB - 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 yieldthe 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 atransition metal-halogen bond.

U2 - 10.1039/c7dt04593j

DO - 10.1039/c7dt04593j

M3 - Article (Academic Journal)

C2 - 29417116

VL - 47

SP - 2759

EP - 2768

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 8

ER -

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

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