Multimetallic Gold–Iron Compounds Based on Aurated Ferrocenes

Meyer, Nadine Sabra; Schucht, Heike; Lehmann, Christian W.; Weibert, Bernhard; Winter, Rainer F.; Mohr, Fabian

doi:10.1002/ejic.201601458

Cited by 6 publications

(1 citation statement)

References 39 publications

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“…Recently, an alternative synthesis was also reported, involving the transmetallation of various (phosphine)gold(I) bromide compounds with arylboronic acids in the presence of base to yield the monosubstituted ferrocene compound 16 and diphosphine derivative 24. 86,96 The unusual dinuclear chiral complex 25 was synthesised from Considering the observation that the (phosphine)gold(I) fragment is σ-isolobal with a proton, 97 the reaction shown in Scheme 5 is remarkably similar to the ring-opening protonolysis of sila [1]ferrocenophanes by HCl (Scheme 1). The ring-opening reaction of dimethylsila [1]ferrocenophane 1 by ClAuPR 3 demonstrates a novel route to gold-substituted ferrocenes, in which further functionalisation may be performed by exploiting the nucleophilicity of the chlorosilane substituent.…”

Section: Scheme 5 Addition Of Au-cl Across the Cp Ipso -Si Bond In 1 mentioning

confidence: 99%

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

et al. 2018

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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-CH)Si(H)TMP] (12) (TMP = 2,2,6,6-tetramethylpiperidyl) towards the hydride-abstraction reagent trityl tetrakis(pentafluorophenyl)borate ([CPh][B(CF)]) was explored. This yielded the unusual dinuclear species [Fe(η-CH)Si(TMP·H)(η-CH)Fe(η-CH)Si(H)TMP][B(CF)] [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-CH)SiMe] (1) with the Au(i) species AuCl(PMe). This was found to result in addition of the Au-Cl bond across the Cp-Si bond to yield the ring-opened species [1'-(chlorodimethylsilyl)-ferrocenyl](trimethylphosphine)gold(i), [Fe(CHSiMeCl){CHAu(PMe)}] (14). This represents the first example of ring-opening addition of a metallocenophane with a reagent possessing a transition metal-halogen bond.

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Section: Scheme 5 Addition Of Au-cl Across the Cp Ipso -Si Bond In 1 mentioning

confidence: 99%

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

et al. 2018

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Asymmetrically Difunctionalized 1,1′‐Ferrocenyl Metalloligands and Their Transition Metal Complexes

et al. 2022

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The synthesis and full characterization of novel 1,1′‐difunctionalized ferrocene metalloligands is described. While one cyclopentadienyl ring has been functionalized with 2,2′‐bipyridine for secondary coordination, the second Cp ring has been decorated with different aryl moieties containing electron withdrawing groups such as 4‐(CF3)C6H4 (2A) 3,5‐(CF3)2C6H3 (2B) or 4‐(NO2)C6H4 (2C). The newly developed metalloligands were reacted with [Pd(cod)Cl2] (3A–C), CuCl2 (4A–C) and trans‐[(PPh3)2Ni(Mes)Br] (5A,B) to obtain the corresponding square‐planar and dimeric square‐pyramidal complexes. The electrochemical behaviour of the ligands and complexes was investigated with the aid of cyclic voltammetry and compared with the corresponding monofunctionalized derivatives. The influence of the implemented functional groups on the nickel complexes was then confirmed for the reductive elimination reaction of an aryl ether induced by oxidation of the corresponding methoxides (6A,B,D). The experimental findings are supported by quantum chemical calculations.

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