vic-Disulfoxides and OS-sulfenyl sulfinates

Freeman, Fillmore

doi:10.1021/cr00060a002

Cited by 113 publications

(73 citation statements)

References 65 publications

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“…have long been recognized as unstable intermediates in the electrophilic oxidation of disulfides [1][2][3] until our success in 1999 with the isolation and unambiguous structure determination of tetrathiolane 2,3-dioxide 1, which has a -S(O)-S(O)-bond. [4,5] Since then we have reported on isolable vic-disulfoxides 2-4.…”

Section: Vic-disulfoxides [Rs(o)s(o)r]mentioning

confidence: 99%

“…[4,5] Since then we have reported on isolable vic-disulfoxides 2-4. [6][7][8][9][10] 3-(1-Adamantyl)-3-tert-butyldithiirane trans-1,2-dioxide (4) is the first three-membered vic-disulfoxide synthesized by the oxidation of the corresponding dithiirane 1-oxide 5 with an acetone solution of dimethyldioxirane (DMD) [Equation (1)]. [9] An interesting reaction of 4 is its decomposition in refluxing chloroform as shown in Scheme 1 to give sulfine 6 and sulfur monoxide (SO) by the main path.…”

Section: Vic-disulfoxides [Rs(o)s(o)r]mentioning

confidence: 99%

“…However, a single, yellow crystal suitable for X-ray analysis was obtained. 1 X-ray Crystallography: X-ray crystallographic analyses were performed with a Mac Science DIP3000 diffractometer (for 14) or a Bruker AXS SMART diffractometer (for others) with a graphitemonochromated Mo-K α radiation (λ = 0.71073 Å). The structures were solved by direct methods and refined with full-matrix leastsquares (SHELXL-97 [46] ) using all independent reflections.…”

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confidence: 99%

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Preparation of 3,3‐Di‐tert‐butylthiirane trans‐1,2‐Dioxide and Its Reaction with a Platinum(0) Complex To Give a (Disulfenato)platinum(II) Complex: Regioselectivity of the Oxidation of a Related (Sulfenato–thiolato)platinum(II) Complex

2007

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A three‐membered vic‐disulfoxide, 3,3‐di‐tert‐butyldithiirane trans‐1,2‐dioxide (8), was synthesized by oxidation of the corresponding dithiirane 1‐oxide 15 in high yield. Treatment of 8 and 15 with a platinum(0) complex, [(Ph3P)2Pt(η2‐C2H4)], yielded the (disulfenato)PtII complex 18 and the (sulfenato–thiolato)PtII complex 14, respectively, in high yields. Oxidation of the sulfenato–thiolato complex 14 with an acetone solution of dimethyldioxirane (DMD) took place at the sulfenato sulfur atom to yield the (sulfinato–thiolato)PtII complex 19, while the oxidation with CF3CO3H occurred at the thiolato‐sulfur atom leading to the disulfenato complex 18. Oxidation of 14 with MCPBA formed both 18 and 19. The position of oxidation on 14 with DMD was dependent on the acidity of a coexisting acid. Thus, oxidation of 14 with DMD/CF3CO2H provided 18 and that with DMD/PhCO2H gave 19. Oxidation of 14 with an excess amount of DMD yielded the (disulfonato)PtII complex 20.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Vic-disulfoxides [Rs(o)s(o)r]mentioning

confidence: 99%

Section: Vic-disulfoxides [Rs(o)s(o)r]mentioning

confidence: 99%

mentioning

confidence: 99%

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Preparation of 3,3‐Di‐tert‐butylthiirane trans‐1,2‐Dioxide and Its Reaction with a Platinum(0) Complex To Give a (Disulfenato)platinum(II) Complex: Regioselectivity of the Oxidation of a Related (Sulfenato–thiolato)platinum(II) Complex

2007

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“…Formation of the disulfide linkage can be induced [25][26][27], and the dithiolate (AuS) can be oxidized into disulfoxide (AuSO), disulfone (AuSO 2 ), or disulfonate (AuSO 3 ) groups [28,29]. In a previous study, we predicted that the formation of the disulfide bonds would not affect the switching behavior of the junction at least at moderate bias voltages [18].…”

Section: Introductionmentioning

confidence: 98%

“…We first calculated the most stable structures of two forms (cyclic and acyclic) of 1,2-dithiolane and 1,2-disulfoxides in the gas phase (Section 3.1) and positioned the optimized gasphase structures on Au 28 clusters representing Au(111) surfaces and re-optimized the geometry on the Au 28 clusters (Section 3.2). The optimized adsorption structures were then employed to build unit cells representing model junction devices (Au-dithiolane-Au and Au-disulfoxide-Au) and the I-V curves were calculated for these junction devices (Section 3.3).…”

Section: Introductionmentioning

confidence: 99%

A DFT study on molecular junction devices with cyclic disulfide anchors: Effect of anchor oxidation on electron transport

Jang

2010

Int J of Quantum Chemistry

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A molecular-scale electronic device can be built with programmable molecular switches sandwiched between two electrodes. A cyclic disulfide, 1,2-dithiolane, is a promising anchor group for attaching molecules to gold electrodes in such molecular junction devices, since its dithiol-Au linkage (with the disulfide bond broken) can provide added stabilities and reduced current fluctuations. However, operations of the molecular switches under redox conditions might lead to redox processes involving the AuAS bonds at the contact. Formation of the disulfide linkage can be induced, and the dithiolate group (AuS) can be converted into disulfoxide (AuSO) or disulfone (AuSO 2 ) groups. Coexistence of these various oxidation states at the contact or the conversion between them can be a potential source of current fluctuation in the junction. However, our nonequilibrium Green's function calculations combined with the density functional theory show that the molecular junctions with different oxidation states of the 1,2-dithiolane alligator clips to two gold electrodes exhibit essentially the same insulating current-voltage characteristics at moderate bias voltages. Therefore, the robustness of the molecular junctions would not be affected by the state change of the disulfide alligator clips at the contact.

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