9H-Fluorene-9-carbodithioic acids and dithioates. First isolation and characterization of a gem-enedithiol

Vicente, José; González‐Herrero, Pablo; Garcı́a-Sánchez, Yolanda; Pérez‐Cadenas, María

doi:10.1016/j.tetlet.2004.09.180

Cited by 12 publications

(13 citation statements)

References 27 publications

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“…The importance of such O−H⋅⋅⋅O hydrogen bond activation of COX is reflected by the fact, that CS 2 is only inserted once, not twice into CH‐bonds of Cat[Cp] under similar conditions, plausibly a matter of weak or non‐existent S−H⋅⋅⋅S hydrogen bond interaction [54,58,59] …”

Section: Resultsmentioning

confidence: 99%

Highly Selective Ortho‐Directed Dicarboxylation of Cyclopentadiene by Methylcarbonates and CO₂ or COS – First Insight into Co‐ordination Chemistry of New Ambident Ligands

Vollgraff

2021

Chemistry A European J

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This research presents the highly regioselective syntheses of 1,2‐dicarboxylated cyclopentadienide salts [Cat]2[C5H3(CO2)2H] by reaction of a variety of organic cation methylcarbonate salts [Cat]OCO2Me (Cat=NR4+, PR4+, Im+) with cyclopentadiene (CpH) or by simply reacting organic cation cyclopentadienides Cat[Cp] (Cat=NR4+, PR4+, Im+) with CO2. One characteristic feature of these dianionic ligands is the acidic proton delocalized in an intramolecular hydrogen bridge (IHB) between the two carboxyl groups, as studied by 1H NMR spectroscopy and XRD analyses. The reaction cannot be stopped after the first carboxylation. Therefore, we propose a Kolbe‐Schmitt phenol‐carboxylation related mechanism where the acidic proton of the monocarboxylic acid intermediate plays an ortho‐directing and CO2 activating role for the second kinetically accelerated CO2 addition step exclusively in ortho position. The same and related thiocarboxylates [Cat]2[C5H3(COS)2H] are obtained by reaction of COS with Cat[Cp] (Cat=NR4+, PR4+, Im+). A preliminary study on [Cat]2[C5H3(CO2)2H] reveals, that its soft and hard coordination sites can selectively be addressed by soft Lewis acids (Mo0, Ru2+) and hard Lewis acids (Al3+, La3+).

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Section: Resultsmentioning

confidence: 99%

Highly Selective Ortho‐Directed Dicarboxylation of Cyclopentadiene by Methylcarbonates and CO₂ or COS – First Insight into Co‐ordination Chemistry of New Ambident Ligands

Vollgraff

2021

Chemistry A European J

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“…Solvents were dried by standard methods and distilled under nitrogen before use. The compounds [Cu(NCMe) 4 ]PF 6 [63] and (pipH)[(tBu-Hfy)CS 2 ] [54] (1) were prepared following published procedures. All other reagents were obtained from commercial sources and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

“…The 1 H and 13 C{ 1 H} NMR spectra of complexes 2 and 3a-e show one set of signals for the protons and carbon atoms of the dithioato ligand, which are slightly modified with respect to those of the free dithioate 1, [54] with the 9-H resonance in the range δ = 5.35-5.68 ppm and the CS 2 resonance in the range δ = 251.5-259.3 ppm. On the basis of these data, complex 2 most probably has a highly symmetrical oligomeric structure (see above).…”

Section: Nmr Spectramentioning

confidence: 98%

Copper Complexes with (2,7‐Di‐tert‐butylfluoren‐9‐ylidene)methanedithiolate: Oxidatively Promoted Dithioate Condensation

et al. 2005

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“…At the same time, Pianka and coworkers established a synthesis of a dithiolate derived from fluorene, Na 2 [FluoCS 2 ] [17] . Vicente and coworkers considered [FluoCS 2 ] 2− as ligand for coordination of group 10 to 11 metals and for luminescence studies [8,20–24] . As consequence of the conjugated Fluo system, the ligand shows a stronger S ‐donor character towards the central metal atom compared to other thiolates, e. g. 1,1‐ethylendithiolates.…”

Section: Introductionmentioning

confidence: 99%

“…The S‐donor strength is tunable by substituents in its Fluo backbone [8] . Again, the ligand [FluoCS 2 ] 2− was not studied in combination with main group metals, the focus was on the investigation of homo‐ and heteroleptic [25] late transition metal complexes [8,20,22–24] and clusters [21] …”

Section: Introductionmentioning

confidence: 99%

Cyclopentadienylidene‐ and Fluoren‐9‐ylidene‐methane‐1,1‐dithiolato Metalates of Tin, Indium and Bismuth

Vollgraff

Michel

2021

Eur J Inorg Chem

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Quaternary ammonium and phosphonium stannates(II), indates(III) and bismuthates(III) displaying dianionic S,S dithiolate chelate ligands [CpCS2]2− and [FluoCS2]2− (Cp=C5H4, Fluo=C13H8) are described. With Sn(II) as central template ion, homoleptic metalates Cat2[Sn(CpCS2)2], with In(III) and Bi(III), highly charged Cat3[In(CpCS2)3] and Cat3[Bi(CpCS2)3] were obtained. A complementary series was characterized for fluoren‐9‐ylidene‐derived metalates Cat2[(FluoCS2)2Sn], Cat3[(FluoCS2)3In] and Cat3[Bi(FluoCS2)3]. Heteroleptic indate(III) NBu4[CpCS2InMe2] (3‐NBu4) and homoleptic [PPh4]3[In(CpCS2)3] (6‐PPh4) as well as stannates(II) [PPh4]2[Sn(CpCS2)2] (5‐PPh4) and [NBu4]2[Sn(FluoCS2)2] (9‐NBu4) were XRD structurally characterized. Reaction of electron‐rich ligand Na2(FluoCS2) with SnCl4 did not lead to an expected stannate(IV) but to a redox reaction and metal free 3,5‐di(9H‐fluorene‐9‐ylidene)‐1,2,4‐trithiolane (12), which was characterized by XRD analysis. The title compounds are related to much better investigated dithiocarbamato(2‐) complexes, well‐established precursors for thermal metal sulfide depositions. In this respect, an explorative DSC‐TGA measurement following the thermal decay of [PPh4]3[(CpCS2)3In] (6‐PPh4) revealed the formation of β‐In2S3 at relatively high temperatures, proven by PXRD.

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9H-Fluorene-9-carbodithioic acids and dithioates. First isolation and characterization of a gem-enedithiol

Cited by 12 publications

References 27 publications

Highly Selective Ortho‐Directed Dicarboxylation of Cyclopentadiene by Methylcarbonates and CO₂ or COS – First Insight into Co‐ordination Chemistry of New Ambident Ligands

Highly Selective Ortho‐Directed Dicarboxylation of Cyclopentadiene by Methylcarbonates and CO₂ or COS – First Insight into Co‐ordination Chemistry of New Ambident Ligands

Copper Complexes with (2,7‐Di‐tert‐butylfluoren‐9‐ylidene)methanedithiolate: Oxidatively Promoted Dithioate Condensation

Cyclopentadienylidene‐ and Fluoren‐9‐ylidene‐methane‐1,1‐dithiolato Metalates of Tin, Indium and Bismuth

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9H-Fluorene-9-carbodithioic acids and dithioates. First isolation and characterization of a gem-enedithiol

Cited by 12 publications

References 27 publications

Highly Selective Ortho‐Directed Dicarboxylation of Cyclopentadiene by Methylcarbonates and CO2 or COS – First Insight into Co‐ordination Chemistry of New Ambident Ligands

Highly Selective Ortho‐Directed Dicarboxylation of Cyclopentadiene by Methylcarbonates and CO2 or COS – First Insight into Co‐ordination Chemistry of New Ambident Ligands

Copper Complexes with (2,7‐Di‐tert‐butylfluoren‐9‐ylidene)methanedithiolate: Oxidatively Promoted Dithioate Condensation

Cyclopentadienylidene‐ and Fluoren‐9‐ylidene‐methane‐1,1‐dithiolato Metalates of Tin, Indium and Bismuth

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Highly Selective Ortho‐Directed Dicarboxylation of Cyclopentadiene by Methylcarbonates and CO₂ or COS – First Insight into Co‐ordination Chemistry of New Ambident Ligands

Highly Selective Ortho‐Directed Dicarboxylation of Cyclopentadiene by Methylcarbonates and CO₂ or COS – First Insight into Co‐ordination Chemistry of New Ambident Ligands