Alk‐2‐ynyl Trimethylsilyl Chalcogenoethers by Nucleophilic Substitution of Propargyl Bromides

Taher, Deeb; Wallbank, Andrew I.; Turner, Elizabeth; Cuthbert, Heather L.; Corrigan, John F.

doi:10.1002/ejic.200600583

Cited by 24 publications

(18 citation statements)

References 60 publications

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“…CH 2 Cl 2 and CHCl 3 , purchased from Caledon, were distilled over P 2 O 5 . Starting reagents E-A C H T U N G T R E N N U N G (SiMe 3 ) 2 , [31] Li…”

Section: Methodsmentioning

confidence: 99%

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Ferrocene‐Based Trimethylsilyl Chalcogenide Reagents for the Assembly of Functionalized Metal–Chalcogen Architectures

MacDonald

Eichhöfer

Campana

et al. 2011

Chemistry A European J

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The ferrocene-based trimethylsilyl chalcogenide reagents [FcC(O)OCH(2)CH(2)ESiMe(3)] (2, E=S, 3 E=Se, Fc=[Fe(η(5)-C(5)H(5))(η(5)-C(5)H(4))]) and [FcC(O)NHCH(2)CH(2) SSiMe(3)] (8b) have been synthesized. The reagents were reacted with solubilized transition-metal acetates to yield functionalized complexes and clusters, including the spherical nanocluster [Ag(14)S{SCH(2)CH(2)O(O)CFc)}(12)(PPh(3))(6)] (11, PPh(3) =triphenylphosphine). The complexes were characterized by NMR spectroscopy and X-ray crystallography. The electrochemical behavior of the complexes was explored by cyclic voltammetry and each displayed a single quasi-reversible redox wave with some adsorption to the electrode surface.

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“…CH 2 Cl 2 and CHCl 3 , purchased from Caledon, were distilled over P 2 O 5 . Starting reagents E-A C H T U N G T R E N N U N G (SiMe 3 ) 2 , [31] Li…”

Section: Methodsmentioning

confidence: 99%

“…À (E = S, Se), [31] [FcC(O)OH], [32] [FcC(O)Cl], [10] were prepared and purified according to literature preparations. Celite was dried by heating at 100 8C under vacuum for 48 h. AgOAc was purchased from Strem Chemicals.…”

Section: Methodsmentioning

confidence: 99%

Ferrocene‐Based Trimethylsilyl Chalcogenide Reagents for the Assembly of Functionalized Metal–Chalcogen Architectures

MacDonald

Eichhöfer

Campana

et al. 2011

Chemistry A European J

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“…[11] We have previously employed [CpFeC 5 H 4 SeSiMe 3 ] to tailor cluster surfaces with FcSe À , however cyclic voltammetry together with constant potential electrolysis illustrated that oxidation of the Fe II centers in [Cd 4 (SeFc) 6 Cl 4 ] 2À clusters resulted in the formation of FcSe-SeFc with concomitant degradation of the metal-chalcogen frameworks. [14] The reaction of [FcCH 2 SSiMe 3 ] with Ph 3 P-solubilized AgOAc yields small amounts of [Ag 10 (m 2 -SCH 2 Fc) 10 Single crystals of 1 are highly solvated, fragile, and weakly diffracting, however a satisfactory data set was obtained after screening diffraction data on several samples. [13] with [Li-{SSiMe 3 }].…”

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A Nanoscopic 3D Polyferrocenyl Assembly: The Triacontakaihexa(ferrocenylmethylthiolate) [Ag₄₈(μ₄‐S)₆(μ_2/3‐SCH₂Fc)₃₆]

Ahmar¹,

MacDonald²,

Vijayaratnam³

et al. 2010

Angewandte Chemie

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Strategies for the incorporation of multiple di(h 5 -cyclopentadienyl)iron (ferrocene) fragments onto molecular architectures have advanced on many fronts. Examples of these successes include the functionalization of dendrimers, [1] polymers, [2] and the surfaces of metal nanoparticles [3] and supramolecular assemblies [4] with these redox active moieties. The motivation for these research efforts is driven in part by their potential for applications in fields of conducting polymers, [5] specialty electrodes, [6] and anion recognition. [7] Recently, the effects on the photophysical properties of incorporating surface ferrocenylalkylthiolates on the surfaces of semiconductor quantum dots (CdSe/ZnS) have been deomonstrated, [8] and exploited for the sensing of fluoride ions. [9] Monolayer protected gold nanoparticles with ferrocenylalkylthiolates have also been prepared in order to modulate the electron-inductive properties of the stabilizing ligand shell with "fully ferrocenated" monolayer protected nanoparticles having been recently reported. [3, 6] On a complementary front, recent reports on the preparation of structurally characterized Ag 2 S nanoclusters have illustrated that these too can be stabilized with surface thiolate ligands exclusively. These preparations have offered an entry into large molecular frameworks with an insulating (aryl) ligand shell. [10] With a suitably designed ferrocenyl reagent, it should be possible to use a monodisperse Ag 2 S architecture for the formation of ferrocenyl-passivated semiconductor nanoclusters. Herein we report the facile preparation of polynuclear ferrocenylmethylthiolate complexes including the high yield synthesis of the redox active nanocluster [Ag 48 (m 4 -S) 6 (m 2/3 -SCH 2 Fc) 36 ] (1).The high solubility of trimethylsilylchalcogenide reagents RESiMe 3 (E = S, Se, Te) allows for the homogeneous reaction conditions required to prepare and crystallize nanoscopic metal-chalcogen complexes. They react with metal carbox-ylates to afford Me 3 SiO 2 CR, which does not interfere with product crystallizations. [11] We have previously employed [CpFeC 5 H 4 SeSiMe 3 ] to tailor cluster surfaces with FcSe À , however cyclic voltammetry together with constant potential electrolysis illustrated that oxidation of the Fe II centers in [Cd 4 (SeFc) 6 Cl 4 ] 2À clusters resulted in the formation of FcSe-SeFc with concomitant degradation of the metal-chalcogen frameworks. [12] The incorporation of one methylene spacer unit between the cyclopentadienyl ring and the chalcogen center was chosen to avoid potential oxidative degradation of the cluster, and where the short À CH 2 À spacer would likely not interfere with the formation of crystallographically ordered structures. [CpFeC 5 H 4 CH 2 SSiMe 3 ] ([FcCH 2 SSiMe 3 ]) can be prepared from [CpFeC 5 H 4 CH 2 Cl] [13] with [Li-{SSiMe 3 }]. [14]The reaction of [FcCH 2 SSiMe 3 ] with Ph 3 P-solubilized AgOAc yields small amounts of [Ag 10 (m 2 -SCH 2 Fc) 10 (PPh 3 ) 4 ] (see Supporting Information) as yellow crystals and [Ag 48 (...

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“…Celite ® was dried by heating at 120 °C under vacuum for 48 h. All other chemicals were used as received from Alfa Aesar and/or Sigma Aldrich without further purification. Starting reagents Li[SSiMe 3 ], [Li( N , N ′‐tmeda)] 2 [Mn(SSiMe 3 ) 4 ], [Mn(CH 3 CN) 2 (OTf) 2 ], [PdCl 2 (dppp)], and [Pd(OAc) 2 (dppp)] were synthesized using literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Metal Trimethylsilylthiolates for the Synthesis of Trinuclear MnPd₂ Complexes

Rozic

Fard

Najafabadi

et al. 2017

Zeitschrift anorg allge chemie

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The manganese(II)‐palladium(II)‐sulfide complex [MnCl2(μ3‐S)2Pd2(dppp)2] (2) was prepared from the reaction of [PdCl2(dppp)] with [Li(N,N'‐tmeda)]2[Mn(SSiMe3)4] (2) in a 2:1 ratio under mild conditions. The new trimethylsilylthiolate complex [Pd(dppp)(SSiMe3)2] (3) was synthesized from the reaction of [Pd(dppp)(OAc)2] with two equivalents of Li[SSiMe3]; this was then used in a reaction with [Mn(CH3CN)2(OTf)2] to form the manganese(II)‐palladium(II)‐sulfide cluster [Mn(OTf)(thf)2(μ3‐S)2Pd2(dppp)2]OTf (4).

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Alk‐2‐ynyl Trimethylsilyl Chalcogenoethers by Nucleophilic Substitution of Propargyl Bromides

Abstract: Lithium (trimethylsilyl)chalcogenolates have been generated and used to prepare a series of alk-2-ynyl trimethylsilyl chalcogenoethers from the corresponding propargyl bromides in good yield. The thermal decomposition of the telluroethers has also been studied.

Cited by 24 publications

References 60 publications

Ferrocene‐Based Trimethylsilyl Chalcogenide Reagents for the Assembly of Functionalized Metal–Chalcogen Architectures

Ferrocene‐Based Trimethylsilyl Chalcogenide Reagents for the Assembly of Functionalized Metal–Chalcogen Architectures

A Nanoscopic 3D Polyferrocenyl Assembly: The Triacontakaihexa(ferrocenylmethylthiolate) [Ag₄₈(μ₄‐S)₆(μ_2/3‐SCH₂Fc)₃₆]

Metal Trimethylsilylthiolates for the Synthesis of Trinuclear MnPd₂ Complexes

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Alk‐2‐ynyl Trimethylsilyl Chalcogenoethers by Nucleophilic Substitution of Propargyl Bromides

Abstract: Lithium (trimethylsilyl)chalcogenolates have been generated and used to prepare a series of alk-2-ynyl trimethylsilyl chalcogenoethers from the corresponding propargyl bromides in good yield. The thermal decomposition of the telluroethers has also been studied.

Cited by 24 publications

References 60 publications

Ferrocene‐Based Trimethylsilyl Chalcogenide Reagents for the Assembly of Functionalized Metal–Chalcogen Architectures

Ferrocene‐Based Trimethylsilyl Chalcogenide Reagents for the Assembly of Functionalized Metal–Chalcogen Architectures

A Nanoscopic 3D Polyferrocenyl Assembly: The Triacontakaihexa(ferrocenylmethylthiolate) [Ag48(μ4‐S)6(μ2/3‐SCH2Fc)36]

Metal Trimethylsilylthiolates for the Synthesis of Trinuclear MnPd2 Complexes

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A Nanoscopic 3D Polyferrocenyl Assembly: The Triacontakaihexa(ferrocenylmethylthiolate) [Ag₄₈(μ₄‐S)₆(μ_2/3‐SCH₂Fc)₃₆]

Metal Trimethylsilylthiolates for the Synthesis of Trinuclear MnPd₂ Complexes