Synthesis of 4,5‐Dimethyl‐1,3‐Dithiol‐2‐One

Chandrasekaran, P.; Donahue, James P.

doi:10.1002/0471264229.os086.32

Cited by 3 publications

(3 citation statements)

References 25 publications

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“…■ EXPERIMENTAL SECTION General Considerations. Literature procedures were employed for the syntheses of 1,2-bis(diphenylphosphino)benzene (dppb), 16 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz), 17 disodium 1,2dicyano-ene-1,2-dithiolate (Na 2 (S 2 C 2 (CN) 2 ), Na 2 mnt), 18 4,5-dimethyl-1,3-dithiol-2-one, 19 4,5-bis(4-methoxyphenyl)-1,3-dithiol-2-one, 20 2,2-dimethyl-4,5-dicyano-1,3,2-dithiastannole ([(mnt)SnMe 2 ]), 21 2,2dimethyl-4,5-bis(4-methoxyphenyl)-1,3,2-dithiastannole ([(adt)-SnMe 2 ]), 20 2,2-dimethyl-4,5-dimethyl-1,3,2-dithiastannole ([(mdt)-SnMe 2 ]), 22 2,2-di-n-butyl-4,5-dimethyl-1,3,2-dithiastannole ([(mdt)-Sn n Bu 2 ]), 22 [Cl 2 M(dppb)] (M = Ni, 23 Pd 24 ), [NiCl 2 (dme)] 25 (dme = 1,2-dimethoxyethane), [Cl 2 Pt(μ-tpbz)PtCl 2 ], 26 [M(pdt) 2 ] 27 (pdt = 1,2-diphenyl-1,2-ethylenedithiolate; M = Ni, Pd, Pt), [PdCl 2 (cod)] (cod = 1,5-cyclooctadiene), 28 [(adt)Pd(dppb)], 15 tpbz)Pd(adt)] (18; adt = 1,2-di-p-anisyl-1,2-ethylenedithiolate). 15 All other reagents were purchased from commercial sources and used as received.…”

Section: ■ Introductionmentioning

confidence: 99%

Redox-Active Metallodithiolene Groups Separated by Insulating Tetraphosphinobenzene Spacers

et al. 2018

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Compounds of the type [(SCR)M(μ-tpbz)M(SCR)] (R = CN, Me, Ph, p-anisyl; M = Ni, Pd, Pt; tpbz = 1,2,4,5-tetrakis(diphenylphosphino)benzene) have been prepared by transmetalation with [(SCR)SnR'] reagents, by direct displacement of dithiolene ligand from [M(SCR)] with 0.5 equiv of tpbz, or by salt metathesis using Na[SC(CN)] in conjunction with XM(μ-tpbz)MX (X = halide). X-ray crystallography reveals a range of topologies (undulating, chair, bowed) for the (SC)M(PCP)M(SC) core. The [(SCR)M(μ-tpbz)M(SCR)] (R = Me, Ph, p-anisyl) compounds support reversible or quasireversible oxidations corresponding to concurrent oxidation of the dithiolene terminal ligands from ene-1,2-dithiolates to radical monoanions, forming [(SSCR)M(μ-tpbz)M(SSCR)]. The R = Ph and p-anisyl compounds support a second, reversible oxidation of the dithiolene ligands to their α-dithione form. In contrast, [(SC(CN))Ni(tpbz)Ni(SC(CN))] sustains only reversible, metal-centered reductions. Spectroscopic examination of [(SSC( p-anisyl))Ni(μ-tpbz)Ni(SSC( p-anisyl))] by EPR reveals a near degenerate singlet-triplet ground state, with spectral simulation revealing a remarkably small dipolar coupling constant of 18 × 10 cm that is representative of an interspin distance of 11.3 Å. This weak interaction is mediated by the rigid tpbz ligand, whose capacity to electronically insulate is an essential quality in the development of molecular-based spintronic devices.

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Section: ■ Introductionmentioning

confidence: 99%

Redox-Active Metallodithiolene Groups Separated by Insulating Tetraphosphinobenzene Spacers

et al. 2018

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“…Synthesis of TMTTP and Preparation of Radical Cation Salts. The desired TMTTP was not yielded by the reaction conditions of 1,3-dithiol-2-thione fused with dimethyl-TTF (1) 16 and two or four equimolar amounts of 4,5dimethyl-1,3-dithiol-2-one (2) 47,48 in the presence of trimethyl phosphite. When 10 equimolar amounts of 2 were used, the desired TMTTP was obtained in a 5.0% yield, and the yield was improved a little by 5.6 and 9.3% using 20 and 30 equimolar amounts of 2, respectively (Scheme 1 and Table S1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Synthesis of TMTTP. To a mixture of 116 (500 mg, 1.48 mmol) and 247,48 (6.47 g, 44.3 mmol) in toluene (35 mL) was added trimethyl phosphite (35 mL), and the solution was stirred at 100 °C for 2 h. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. Methanol was added, and then, the resulting brown precipitate was collected by filtration and washed with methanol.…”

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Organic Molecular Conductors Based on Tetramethyl-TTP: Structural and Electrical Properties Modulated by the Anion Size and Shape

et al. 2022

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The tetramethyl derivative of bis-fused tetrathiafulvalene, 2,5-bis(4,5-dimethyl-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (TMTTP), has been successfully synthesized. Most of the radical cation salts consisting of TMTTP feature a high electrical conductivity of σrt = 101 to 102 S cm–1 on a single crystal. The anion shape and size of TMTTP conductors modulate the electrical properties. The PF6 – and AsF6 – salts exhibit metallic conductivity down to 10 K, while the ReO4 – and AuI2 – salts show metal-to-insulator (MI) transition at 126 and 11 K, respectively. Single-crystal X-ray structure analysis of (TMTTP)2X (X = PF6, AsF6, BF4, and ReO4) and (TMTTP)3AuI2 reveals that the donor packing motif is categorized as the so-called β-type. The tight-binding band calculations of (TMTTP)2X (X = ReO4, BF4, PF6, and AsF6) suggest these salts are characterized by quasi-one-dimensional Fermi surfaces. The band calculation based on X-ray structure analysis of (TMTTP)2ReO4 at 100 K demonstrates that the MI transition of this salt is associated with the charge ordering with the zigzag stripe pattern.

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The dithiolene ligand and tetrathiafulvalene precursor molecules 4,5-bis(bromomethyl)-1,3-dithiol-2-one and 4,5-bis[(dihydroxyphosphoryl)methyl]-1,3-dithiol-2-one

et al. 2011

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The crystal structures of 4,5-bis(bromomethyl)-1,3-dithiol-2-one, C(5)H(4)Br(2)OS(2), (I), and 4,5-bis[(dihydroxyphosphoryl)methyl]-1,3-dithiol-2-one, C(5)H(8)O(7)P(2)S(2), (II), occur with similar unit cells in the same monoclinic space group. Both molecules reside on a twofold symmetry axis coincident with the C=O bond, so that the substituents in the 4- and 5-positions project above and below the plane of the 1,3-dithiol-2-one ring. In both structures, the molecules align themselves in a head-to-tail fashion along the b axis, and these rows of molecules then stack, with alternating directionality, along the c axis. For (II), an extensive network of intermolecular hydrogen bonds occurs between molecules within the same stack and between adjacent stacks. Each -CH(2)P(O)(OH)(2) group participates in four hydrogen bonds, twice as donor and twice as acceptor.

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Synthesis of 4,5‐Dimethyl‐1,3‐Dithiol‐2‐One

Abstract: O‐ Isopropyl S‐ 3‐Oxobutan‐2‐yl dithicarbonate 2‐Butanone Potassium O‐ isopropylxanthate 4,5‐Dimethyl‐1,3‐dithiol‐2‐one

Cited by 3 publications

References 25 publications

Redox-Active Metallodithiolene Groups Separated by Insulating Tetraphosphinobenzene Spacers

Redox-Active Metallodithiolene Groups Separated by Insulating Tetraphosphinobenzene Spacers

Organic Molecular Conductors Based on Tetramethyl-TTP: Structural and Electrical Properties Modulated by the Anion Size and Shape

The dithiolene ligand and tetrathiafulvalene precursor molecules 4,5-bis(bromomethyl)-1,3-dithiol-2-one and 4,5-bis[(dihydroxyphosphoryl)methyl]-1,3-dithiol-2-one

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