Do quaternary sulfur dications exist?Why are many silver salts insoluble?Stability of Sulfides - backbonding?Why is an ionic bond a chemical and not a physical bond?Determine polarity of covalent bond with formal chargeWhy is an S-S bond stronger than an O-O bond?Why do nitro groups preferentially bond through the nitrogen rather than the oxygen?Can heteroatoms with lone pairs be chiral centres?Why can't oxalate ion donate two pairs of electrons from the two double-bonded oxygen atomsWill the carboxylate groups of the citrate anion undergo hydrogen bonding?Why does 1,3-dichloropropane not show stereoisomerism?

Which "exotic salt" can lower water's freezing point by –70 °C?

Explaining intravenous drug abuse to a small child

How to use awk to extract data from a file based on the content of another file?

Efficient deletion of specific list entries

Copper as an adjective to refer to something made of copper

Was there a dinosaur-counter in the original Jurassic Park movie?

How to deal with employer who keeps me at work after working hours

Can an Iranian citizen enter the USA on a Dutch passport?

What's the 2-minute timer on mobile Deutsche Bahn tickets?

Primes in a Diamond

How to say something covers all the view up to the horizon line?

Can a good but unremarkable PhD student become an accomplished professor?

How would you say "You forget wearing what you're wearing"?

What does のそ mean on this picture?

What is monoid homomorphism exactly?

What word describes the sound of an instrument based on the shape of the waveform of its sound?

GitLab account hacked and repo wiped

What is the thing used to help pouring liquids called?

Why are condenser mics so much more expensive than dynamics?

How is trade in services conducted under the WTO in the absence of the Doha conclusion?

Find the area of the smallest rectangle to contain squares of sizes up to n

Given a safe domain, are subdirectories safe as well?

Subnumcases as a part of align

HSA - Continue to Invest?



Do quaternary sulfur dications exist?


Why are many silver salts insoluble?Stability of Sulfides - backbonding?Why is an ionic bond a chemical and not a physical bond?Determine polarity of covalent bond with formal chargeWhy is an S-S bond stronger than an O-O bond?Why do nitro groups preferentially bond through the nitrogen rather than the oxygen?Can heteroatoms with lone pairs be chiral centres?Why can't oxalate ion donate two pairs of electrons from the two double-bonded oxygen atomsWill the carboxylate groups of the citrate anion undergo hydrogen bonding?Why does 1,3-dichloropropane not show stereoisomerism?













3












$begingroup$


We know that sulfur can form sulfides $ceR2S$, with two substituents bonded to it. The simplest example of this would be hydrogen sulfide.



However, sulfur can also form sulfonium ions $ceR3S+$, where 3 substituents are attached to the sulfur atom and a negatively-charged counteranion is present.



What I am asking is whether there is such a thing as sulfur bonded to 4 substituents, with each bond being a single bond, with 2 counteranions (either $ce(R4S^2+)(X^2-)$ or $ce(R4S^2+)(X^-)2$). Is there such a thing as that or something similar?










share|improve this question











$endgroup$
















    3












    $begingroup$


    We know that sulfur can form sulfides $ceR2S$, with two substituents bonded to it. The simplest example of this would be hydrogen sulfide.



    However, sulfur can also form sulfonium ions $ceR3S+$, where 3 substituents are attached to the sulfur atom and a negatively-charged counteranion is present.



    What I am asking is whether there is such a thing as sulfur bonded to 4 substituents, with each bond being a single bond, with 2 counteranions (either $ce(R4S^2+)(X^2-)$ or $ce(R4S^2+)(X^-)2$). Is there such a thing as that or something similar?










    share|improve this question











    $endgroup$














      3












      3








      3





      $begingroup$


      We know that sulfur can form sulfides $ceR2S$, with two substituents bonded to it. The simplest example of this would be hydrogen sulfide.



      However, sulfur can also form sulfonium ions $ceR3S+$, where 3 substituents are attached to the sulfur atom and a negatively-charged counteranion is present.



      What I am asking is whether there is such a thing as sulfur bonded to 4 substituents, with each bond being a single bond, with 2 counteranions (either $ce(R4S^2+)(X^2-)$ or $ce(R4S^2+)(X^-)2$). Is there such a thing as that or something similar?










      share|improve this question











      $endgroup$




      We know that sulfur can form sulfides $ceR2S$, with two substituents bonded to it. The simplest example of this would be hydrogen sulfide.



      However, sulfur can also form sulfonium ions $ceR3S+$, where 3 substituents are attached to the sulfur atom and a negatively-charged counteranion is present.



      What I am asking is whether there is such a thing as sulfur bonded to 4 substituents, with each bond being a single bond, with 2 counteranions (either $ce(R4S^2+)(X^2-)$ or $ce(R4S^2+)(X^-)2$). Is there such a thing as that or something similar?







      organic-chemistry inorganic-chemistry ions organosulfur-compounds






      share|improve this question















      share|improve this question













      share|improve this question




      share|improve this question








      edited 1 hour ago









      orthocresol

      40.7k7120252




      40.7k7120252










      asked 2 hours ago









      user73910user73910

      1223




      1223




















          1 Answer
          1






          active

          oldest

          votes


















          3












          $begingroup$

          Ogawa et al. [1] were first to report a crystal structure (CSD-YAFNOI) of a compound with quaternary sulfur, bis(2,2′-biphenylylene)sulfurane:



          bis(2,2′-biphenylylene)sulfurane crystal structure



          Figure 1. Molecular structure of bis(2,2'-biphenylene)sulfurane (CSD-YAFNOI). Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Compound 1 was synthesized as follows (Scheme 1). Dibenzothiophene 5-oxide (200 mg, 1.0 mmol) in anhydrous tetrahydrofuran (THF, 10 ml) was treated with trimethylsilyl trifluoromethanesulfonate (0.25 ml, 1.3 mmol) under an $ceN2$ atmosphere at −78 °C. After stirring at 0 °C for 30 min, the
          mixture was cooled to −78 °C and was treated with $pu1.0 mol dm-3$ 2,2'-dilithiobiphenyl (1.0 ml, 1.0 mmol) in diethyl ether solution. The whole mixture was stirred at −78 °C for 1 h and at 0 °C for 30 min under an $ceN2$ atmosphere. After evaporation of the solvent, the residue was washed with anhydrous diethyl ether (10 ml) and was extracted with anhydrous benzene (10 ml) under an $ceN2$ atmosphere. The solvent was removed under reduced pressure, and the crude product was recrystallized from anhydrous THF at −20 °C to give 1 as orange rods in 96% yield.



          bis(2,2′-biphenylylene)sulfurane synthesis



          Scheme 1 Reagents: i, trimethylsilyl trifluoromethansulfonate in THF;
          ii, 2,2'-dilithiobiphenyl in diethyl ether-THF




          Further work by Sato et al. [2] resulted in a synthesis and crystal structure (CSD-NEDCEE) of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate).



          Structurally, it's a similar compound with a greater, nearly 90° (in contrast to 60° twist angle in neutral bis(2,2′-biphenylylene)sulfurane), twist angle between 2,2′-biphenylylene ligands, however water molecules and $ce[BF4]$-counterions appear heavily disordered:



          bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) crystal structure fragment



          Figure 2. Fragment of the molecular structure of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) (CSD-NEDCEE) showing the bis(2,2′-biphenylylene)sulfuranyl cation. Oxygen atoms from water molecules as well as tetrafluoroborate anions are omitted for clarity. Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Recently, we have succeeded in the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane [10-S-4(C4)] (1) as a stable sulfurane(IV) having only carbon ligands.[…] We considered that this sulfurane would be a suitable precursor to provide the desired dication. Therefore, we tried the reaction of bis(2,2′-biphenylylene)sulfurane (1) with xenon difluoride ($ceXeF2$) in the presence of $ceBF3 * OEt2$ and indeed obtained the bis(2,2′-biphenylylene)sulfurane dication, [8-S4(C4)]²⁺ (2) as an amazingly stable bis(tetrafluoroborate) salt.[…] Here, we communicate the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane dication (2) having only carbon ligands. […]



          The sulfurane 1 was reacted with 1 mol equiv of xenon difluoride in the presence of $ceBF3 * OEt2$ in dry $ceCH3CN$ at −40 °C (Scheme 1). After the solvent was removed at room temperature, the residue was washed with $ceCHCl3$ at room temperature, and bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) (2) was isolated as a stable moisture-insensitive yellow powder in 62% yield.



          bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) synthesis



          Scheme 1




          Subsequently, hexacoordinated derivatives – bis(2,2′-biphenylylene)dimethyl- and diphenylpersulfuranes – were synthesized and their molecular structures were elucidated [3].



          References



          1. Ogawa, S.; Matsunaga, Y.; Sato, S.; Iida, I.; Furukawa, N. First Preparation of a Sulfurane with Four Carbon–Sulfur Bonds: Synthesis and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfurane. J. Chem. Soc., Chem. Commun. 1992, 0 (16), 1141–1142. https://doi.org/10.1039/C39920001141.

          2. Sato, S.; Ameta, H.; Horn, E.; Takahashi, O.; Furukawa, N. First Isolation and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfuranyl Bis(Tetrafluoroborate) [8−S−4(C4)]²⁺. J. Am. Chem. Soc. 1997, 119 (50), 12374–12375. https://doi.org/10.1021/ja971336k.

          3. Sato, S.; Matsunaga, K.; Horn, E.; Furukawa, N.; Nabeshima, T. Isolation and Molecular Structure of the Organo-Persulfuranes [12−S−6(C6)]. J. Am. Chem. Soc. 2006, 128 (21), 6778–6779. https://doi.org/10.1021/ja060497y.





          share|improve this answer











          $endgroup$








          • 2




            $begingroup$
            I think OP is looking for something of the form $ce(R4S^2+)(X^-)2$, which isn't quite the same, albeit quite close...
            $endgroup$
            – orthocresol
            1 hour ago







          • 2




            $begingroup$
            @orthocresol I see; it seems like dx.doi.org/10.1021/ja971336k and dx.doi.org/10.1021/ja060497y would make a better answer then; I'm going to edit the more recent work in within the next hour:)
            $endgroup$
            – andselisk
            1 hour ago












          Your Answer








          StackExchange.ready(function()
          var channelOptions =
          tags: "".split(" "),
          id: "431"
          ;
          initTagRenderer("".split(" "), "".split(" "), channelOptions);

          StackExchange.using("externalEditor", function()
          // Have to fire editor after snippets, if snippets enabled
          if (StackExchange.settings.snippets.snippetsEnabled)
          StackExchange.using("snippets", function()
          createEditor();
          );

          else
          createEditor();

          );

          function createEditor()
          StackExchange.prepareEditor(
          heartbeatType: 'answer',
          autoActivateHeartbeat: false,
          convertImagesToLinks: false,
          noModals: true,
          showLowRepImageUploadWarning: true,
          reputationToPostImages: null,
          bindNavPrevention: true,
          postfix: "",
          imageUploader:
          brandingHtml: "Powered by u003ca class="icon-imgur-white" href="https://imgur.com/"u003eu003c/au003e",
          contentPolicyHtml: "User contributions licensed under u003ca href="https://creativecommons.org/licenses/by-sa/3.0/"u003ecc by-sa 3.0 with attribution requiredu003c/au003e u003ca href="https://stackoverflow.com/legal/content-policy"u003e(content policy)u003c/au003e",
          allowUrls: true
          ,
          onDemand: true,
          discardSelector: ".discard-answer"
          ,immediatelyShowMarkdownHelp:true
          );



          );













          draft saved

          draft discarded


















          StackExchange.ready(
          function ()
          StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fchemistry.stackexchange.com%2fquestions%2f114887%2fdo-quaternary-sulfur-dications-exist%23new-answer', 'question_page');

          );

          Post as a guest















          Required, but never shown

























          1 Answer
          1






          active

          oldest

          votes








          1 Answer
          1






          active

          oldest

          votes









          active

          oldest

          votes






          active

          oldest

          votes









          3












          $begingroup$

          Ogawa et al. [1] were first to report a crystal structure (CSD-YAFNOI) of a compound with quaternary sulfur, bis(2,2′-biphenylylene)sulfurane:



          bis(2,2′-biphenylylene)sulfurane crystal structure



          Figure 1. Molecular structure of bis(2,2'-biphenylene)sulfurane (CSD-YAFNOI). Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Compound 1 was synthesized as follows (Scheme 1). Dibenzothiophene 5-oxide (200 mg, 1.0 mmol) in anhydrous tetrahydrofuran (THF, 10 ml) was treated with trimethylsilyl trifluoromethanesulfonate (0.25 ml, 1.3 mmol) under an $ceN2$ atmosphere at −78 °C. After stirring at 0 °C for 30 min, the
          mixture was cooled to −78 °C and was treated with $pu1.0 mol dm-3$ 2,2'-dilithiobiphenyl (1.0 ml, 1.0 mmol) in diethyl ether solution. The whole mixture was stirred at −78 °C for 1 h and at 0 °C for 30 min under an $ceN2$ atmosphere. After evaporation of the solvent, the residue was washed with anhydrous diethyl ether (10 ml) and was extracted with anhydrous benzene (10 ml) under an $ceN2$ atmosphere. The solvent was removed under reduced pressure, and the crude product was recrystallized from anhydrous THF at −20 °C to give 1 as orange rods in 96% yield.



          bis(2,2′-biphenylylene)sulfurane synthesis



          Scheme 1 Reagents: i, trimethylsilyl trifluoromethansulfonate in THF;
          ii, 2,2'-dilithiobiphenyl in diethyl ether-THF




          Further work by Sato et al. [2] resulted in a synthesis and crystal structure (CSD-NEDCEE) of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate).



          Structurally, it's a similar compound with a greater, nearly 90° (in contrast to 60° twist angle in neutral bis(2,2′-biphenylylene)sulfurane), twist angle between 2,2′-biphenylylene ligands, however water molecules and $ce[BF4]$-counterions appear heavily disordered:



          bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) crystal structure fragment



          Figure 2. Fragment of the molecular structure of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) (CSD-NEDCEE) showing the bis(2,2′-biphenylylene)sulfuranyl cation. Oxygen atoms from water molecules as well as tetrafluoroborate anions are omitted for clarity. Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Recently, we have succeeded in the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane [10-S-4(C4)] (1) as a stable sulfurane(IV) having only carbon ligands.[…] We considered that this sulfurane would be a suitable precursor to provide the desired dication. Therefore, we tried the reaction of bis(2,2′-biphenylylene)sulfurane (1) with xenon difluoride ($ceXeF2$) in the presence of $ceBF3 * OEt2$ and indeed obtained the bis(2,2′-biphenylylene)sulfurane dication, [8-S4(C4)]²⁺ (2) as an amazingly stable bis(tetrafluoroborate) salt.[…] Here, we communicate the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane dication (2) having only carbon ligands. […]



          The sulfurane 1 was reacted with 1 mol equiv of xenon difluoride in the presence of $ceBF3 * OEt2$ in dry $ceCH3CN$ at −40 °C (Scheme 1). After the solvent was removed at room temperature, the residue was washed with $ceCHCl3$ at room temperature, and bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) (2) was isolated as a stable moisture-insensitive yellow powder in 62% yield.



          bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) synthesis



          Scheme 1




          Subsequently, hexacoordinated derivatives – bis(2,2′-biphenylylene)dimethyl- and diphenylpersulfuranes – were synthesized and their molecular structures were elucidated [3].



          References



          1. Ogawa, S.; Matsunaga, Y.; Sato, S.; Iida, I.; Furukawa, N. First Preparation of a Sulfurane with Four Carbon–Sulfur Bonds: Synthesis and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfurane. J. Chem. Soc., Chem. Commun. 1992, 0 (16), 1141–1142. https://doi.org/10.1039/C39920001141.

          2. Sato, S.; Ameta, H.; Horn, E.; Takahashi, O.; Furukawa, N. First Isolation and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfuranyl Bis(Tetrafluoroborate) [8−S−4(C4)]²⁺. J. Am. Chem. Soc. 1997, 119 (50), 12374–12375. https://doi.org/10.1021/ja971336k.

          3. Sato, S.; Matsunaga, K.; Horn, E.; Furukawa, N.; Nabeshima, T. Isolation and Molecular Structure of the Organo-Persulfuranes [12−S−6(C6)]. J. Am. Chem. Soc. 2006, 128 (21), 6778–6779. https://doi.org/10.1021/ja060497y.





          share|improve this answer











          $endgroup$








          • 2




            $begingroup$
            I think OP is looking for something of the form $ce(R4S^2+)(X^-)2$, which isn't quite the same, albeit quite close...
            $endgroup$
            – orthocresol
            1 hour ago







          • 2




            $begingroup$
            @orthocresol I see; it seems like dx.doi.org/10.1021/ja971336k and dx.doi.org/10.1021/ja060497y would make a better answer then; I'm going to edit the more recent work in within the next hour:)
            $endgroup$
            – andselisk
            1 hour ago
















          3












          $begingroup$

          Ogawa et al. [1] were first to report a crystal structure (CSD-YAFNOI) of a compound with quaternary sulfur, bis(2,2′-biphenylylene)sulfurane:



          bis(2,2′-biphenylylene)sulfurane crystal structure



          Figure 1. Molecular structure of bis(2,2'-biphenylene)sulfurane (CSD-YAFNOI). Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Compound 1 was synthesized as follows (Scheme 1). Dibenzothiophene 5-oxide (200 mg, 1.0 mmol) in anhydrous tetrahydrofuran (THF, 10 ml) was treated with trimethylsilyl trifluoromethanesulfonate (0.25 ml, 1.3 mmol) under an $ceN2$ atmosphere at −78 °C. After stirring at 0 °C for 30 min, the
          mixture was cooled to −78 °C and was treated with $pu1.0 mol dm-3$ 2,2'-dilithiobiphenyl (1.0 ml, 1.0 mmol) in diethyl ether solution. The whole mixture was stirred at −78 °C for 1 h and at 0 °C for 30 min under an $ceN2$ atmosphere. After evaporation of the solvent, the residue was washed with anhydrous diethyl ether (10 ml) and was extracted with anhydrous benzene (10 ml) under an $ceN2$ atmosphere. The solvent was removed under reduced pressure, and the crude product was recrystallized from anhydrous THF at −20 °C to give 1 as orange rods in 96% yield.



          bis(2,2′-biphenylylene)sulfurane synthesis



          Scheme 1 Reagents: i, trimethylsilyl trifluoromethansulfonate in THF;
          ii, 2,2'-dilithiobiphenyl in diethyl ether-THF




          Further work by Sato et al. [2] resulted in a synthesis and crystal structure (CSD-NEDCEE) of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate).



          Structurally, it's a similar compound with a greater, nearly 90° (in contrast to 60° twist angle in neutral bis(2,2′-biphenylylene)sulfurane), twist angle between 2,2′-biphenylylene ligands, however water molecules and $ce[BF4]$-counterions appear heavily disordered:



          bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) crystal structure fragment



          Figure 2. Fragment of the molecular structure of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) (CSD-NEDCEE) showing the bis(2,2′-biphenylylene)sulfuranyl cation. Oxygen atoms from water molecules as well as tetrafluoroborate anions are omitted for clarity. Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Recently, we have succeeded in the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane [10-S-4(C4)] (1) as a stable sulfurane(IV) having only carbon ligands.[…] We considered that this sulfurane would be a suitable precursor to provide the desired dication. Therefore, we tried the reaction of bis(2,2′-biphenylylene)sulfurane (1) with xenon difluoride ($ceXeF2$) in the presence of $ceBF3 * OEt2$ and indeed obtained the bis(2,2′-biphenylylene)sulfurane dication, [8-S4(C4)]²⁺ (2) as an amazingly stable bis(tetrafluoroborate) salt.[…] Here, we communicate the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane dication (2) having only carbon ligands. […]



          The sulfurane 1 was reacted with 1 mol equiv of xenon difluoride in the presence of $ceBF3 * OEt2$ in dry $ceCH3CN$ at −40 °C (Scheme 1). After the solvent was removed at room temperature, the residue was washed with $ceCHCl3$ at room temperature, and bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) (2) was isolated as a stable moisture-insensitive yellow powder in 62% yield.



          bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) synthesis



          Scheme 1




          Subsequently, hexacoordinated derivatives – bis(2,2′-biphenylylene)dimethyl- and diphenylpersulfuranes – were synthesized and their molecular structures were elucidated [3].



          References



          1. Ogawa, S.; Matsunaga, Y.; Sato, S.; Iida, I.; Furukawa, N. First Preparation of a Sulfurane with Four Carbon–Sulfur Bonds: Synthesis and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfurane. J. Chem. Soc., Chem. Commun. 1992, 0 (16), 1141–1142. https://doi.org/10.1039/C39920001141.

          2. Sato, S.; Ameta, H.; Horn, E.; Takahashi, O.; Furukawa, N. First Isolation and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfuranyl Bis(Tetrafluoroborate) [8−S−4(C4)]²⁺. J. Am. Chem. Soc. 1997, 119 (50), 12374–12375. https://doi.org/10.1021/ja971336k.

          3. Sato, S.; Matsunaga, K.; Horn, E.; Furukawa, N.; Nabeshima, T. Isolation and Molecular Structure of the Organo-Persulfuranes [12−S−6(C6)]. J. Am. Chem. Soc. 2006, 128 (21), 6778–6779. https://doi.org/10.1021/ja060497y.





          share|improve this answer











          $endgroup$








          • 2




            $begingroup$
            I think OP is looking for something of the form $ce(R4S^2+)(X^-)2$, which isn't quite the same, albeit quite close...
            $endgroup$
            – orthocresol
            1 hour ago







          • 2




            $begingroup$
            @orthocresol I see; it seems like dx.doi.org/10.1021/ja971336k and dx.doi.org/10.1021/ja060497y would make a better answer then; I'm going to edit the more recent work in within the next hour:)
            $endgroup$
            – andselisk
            1 hour ago














          3












          3








          3





          $begingroup$

          Ogawa et al. [1] were first to report a crystal structure (CSD-YAFNOI) of a compound with quaternary sulfur, bis(2,2′-biphenylylene)sulfurane:



          bis(2,2′-biphenylylene)sulfurane crystal structure



          Figure 1. Molecular structure of bis(2,2'-biphenylene)sulfurane (CSD-YAFNOI). Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Compound 1 was synthesized as follows (Scheme 1). Dibenzothiophene 5-oxide (200 mg, 1.0 mmol) in anhydrous tetrahydrofuran (THF, 10 ml) was treated with trimethylsilyl trifluoromethanesulfonate (0.25 ml, 1.3 mmol) under an $ceN2$ atmosphere at −78 °C. After stirring at 0 °C for 30 min, the
          mixture was cooled to −78 °C and was treated with $pu1.0 mol dm-3$ 2,2'-dilithiobiphenyl (1.0 ml, 1.0 mmol) in diethyl ether solution. The whole mixture was stirred at −78 °C for 1 h and at 0 °C for 30 min under an $ceN2$ atmosphere. After evaporation of the solvent, the residue was washed with anhydrous diethyl ether (10 ml) and was extracted with anhydrous benzene (10 ml) under an $ceN2$ atmosphere. The solvent was removed under reduced pressure, and the crude product was recrystallized from anhydrous THF at −20 °C to give 1 as orange rods in 96% yield.



          bis(2,2′-biphenylylene)sulfurane synthesis



          Scheme 1 Reagents: i, trimethylsilyl trifluoromethansulfonate in THF;
          ii, 2,2'-dilithiobiphenyl in diethyl ether-THF




          Further work by Sato et al. [2] resulted in a synthesis and crystal structure (CSD-NEDCEE) of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate).



          Structurally, it's a similar compound with a greater, nearly 90° (in contrast to 60° twist angle in neutral bis(2,2′-biphenylylene)sulfurane), twist angle between 2,2′-biphenylylene ligands, however water molecules and $ce[BF4]$-counterions appear heavily disordered:



          bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) crystal structure fragment



          Figure 2. Fragment of the molecular structure of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) (CSD-NEDCEE) showing the bis(2,2′-biphenylylene)sulfuranyl cation. Oxygen atoms from water molecules as well as tetrafluoroborate anions are omitted for clarity. Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Recently, we have succeeded in the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane [10-S-4(C4)] (1) as a stable sulfurane(IV) having only carbon ligands.[…] We considered that this sulfurane would be a suitable precursor to provide the desired dication. Therefore, we tried the reaction of bis(2,2′-biphenylylene)sulfurane (1) with xenon difluoride ($ceXeF2$) in the presence of $ceBF3 * OEt2$ and indeed obtained the bis(2,2′-biphenylylene)sulfurane dication, [8-S4(C4)]²⁺ (2) as an amazingly stable bis(tetrafluoroborate) salt.[…] Here, we communicate the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane dication (2) having only carbon ligands. […]



          The sulfurane 1 was reacted with 1 mol equiv of xenon difluoride in the presence of $ceBF3 * OEt2$ in dry $ceCH3CN$ at −40 °C (Scheme 1). After the solvent was removed at room temperature, the residue was washed with $ceCHCl3$ at room temperature, and bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) (2) was isolated as a stable moisture-insensitive yellow powder in 62% yield.



          bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) synthesis



          Scheme 1




          Subsequently, hexacoordinated derivatives – bis(2,2′-biphenylylene)dimethyl- and diphenylpersulfuranes – were synthesized and their molecular structures were elucidated [3].



          References



          1. Ogawa, S.; Matsunaga, Y.; Sato, S.; Iida, I.; Furukawa, N. First Preparation of a Sulfurane with Four Carbon–Sulfur Bonds: Synthesis and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfurane. J. Chem. Soc., Chem. Commun. 1992, 0 (16), 1141–1142. https://doi.org/10.1039/C39920001141.

          2. Sato, S.; Ameta, H.; Horn, E.; Takahashi, O.; Furukawa, N. First Isolation and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfuranyl Bis(Tetrafluoroborate) [8−S−4(C4)]²⁺. J. Am. Chem. Soc. 1997, 119 (50), 12374–12375. https://doi.org/10.1021/ja971336k.

          3. Sato, S.; Matsunaga, K.; Horn, E.; Furukawa, N.; Nabeshima, T. Isolation and Molecular Structure of the Organo-Persulfuranes [12−S−6(C6)]. J. Am. Chem. Soc. 2006, 128 (21), 6778–6779. https://doi.org/10.1021/ja060497y.





          share|improve this answer











          $endgroup$



          Ogawa et al. [1] were first to report a crystal structure (CSD-YAFNOI) of a compound with quaternary sulfur, bis(2,2′-biphenylylene)sulfurane:



          bis(2,2′-biphenylylene)sulfurane crystal structure



          Figure 1. Molecular structure of bis(2,2'-biphenylene)sulfurane (CSD-YAFNOI). Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Compound 1 was synthesized as follows (Scheme 1). Dibenzothiophene 5-oxide (200 mg, 1.0 mmol) in anhydrous tetrahydrofuran (THF, 10 ml) was treated with trimethylsilyl trifluoromethanesulfonate (0.25 ml, 1.3 mmol) under an $ceN2$ atmosphere at −78 °C. After stirring at 0 °C for 30 min, the
          mixture was cooled to −78 °C and was treated with $pu1.0 mol dm-3$ 2,2'-dilithiobiphenyl (1.0 ml, 1.0 mmol) in diethyl ether solution. The whole mixture was stirred at −78 °C for 1 h and at 0 °C for 30 min under an $ceN2$ atmosphere. After evaporation of the solvent, the residue was washed with anhydrous diethyl ether (10 ml) and was extracted with anhydrous benzene (10 ml) under an $ceN2$ atmosphere. The solvent was removed under reduced pressure, and the crude product was recrystallized from anhydrous THF at −20 °C to give 1 as orange rods in 96% yield.



          bis(2,2′-biphenylylene)sulfurane synthesis



          Scheme 1 Reagents: i, trimethylsilyl trifluoromethansulfonate in THF;
          ii, 2,2'-dilithiobiphenyl in diethyl ether-THF




          Further work by Sato et al. [2] resulted in a synthesis and crystal structure (CSD-NEDCEE) of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate).



          Structurally, it's a similar compound with a greater, nearly 90° (in contrast to 60° twist angle in neutral bis(2,2′-biphenylylene)sulfurane), twist angle between 2,2′-biphenylylene ligands, however water molecules and $ce[BF4]$-counterions appear heavily disordered:



          bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) crystal structure fragment



          Figure 2. Fragment of the molecular structure of bis(2,2′-biphenylylene)sulfuranyl bis(tetrafluoroborate) (CSD-NEDCEE) showing the bis(2,2′-biphenylylene)sulfuranyl cation. Oxygen atoms from water molecules as well as tetrafluoroborate anions are omitted for clarity. Color code: $color#EEEEEELargebullet~ceH$; $color#909090Largebullet~ceC$; $color#FFFF30Largebullet~ceS$.




          Recently, we have succeeded in the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane [10-S-4(C4)] (1) as a stable sulfurane(IV) having only carbon ligands.[…] We considered that this sulfurane would be a suitable precursor to provide the desired dication. Therefore, we tried the reaction of bis(2,2′-biphenylylene)sulfurane (1) with xenon difluoride ($ceXeF2$) in the presence of $ceBF3 * OEt2$ and indeed obtained the bis(2,2′-biphenylylene)sulfurane dication, [8-S4(C4)]²⁺ (2) as an amazingly stable bis(tetrafluoroborate) salt.[…] Here, we communicate the first isolation and structural determination of bis(2,2′-biphenylylene)sulfurane dication (2) having only carbon ligands. […]



          The sulfurane 1 was reacted with 1 mol equiv of xenon difluoride in the presence of $ceBF3 * OEt2$ in dry $ceCH3CN$ at −40 °C (Scheme 1). After the solvent was removed at room temperature, the residue was washed with $ceCHCl3$ at room temperature, and bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) (2) was isolated as a stable moisture-insensitive yellow powder in 62% yield.



          bis(2,2′-biphenylylene)sulfurane bis(tetrafluoroborate) synthesis



          Scheme 1




          Subsequently, hexacoordinated derivatives – bis(2,2′-biphenylylene)dimethyl- and diphenylpersulfuranes – were synthesized and their molecular structures were elucidated [3].



          References



          1. Ogawa, S.; Matsunaga, Y.; Sato, S.; Iida, I.; Furukawa, N. First Preparation of a Sulfurane with Four Carbon–Sulfur Bonds: Synthesis and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfurane. J. Chem. Soc., Chem. Commun. 1992, 0 (16), 1141–1142. https://doi.org/10.1039/C39920001141.

          2. Sato, S.; Ameta, H.; Horn, E.; Takahashi, O.; Furukawa, N. First Isolation and Molecular Structure of Bis(2,2′-Biphenylylene)Sulfuranyl Bis(Tetrafluoroborate) [8−S−4(C4)]²⁺. J. Am. Chem. Soc. 1997, 119 (50), 12374–12375. https://doi.org/10.1021/ja971336k.

          3. Sato, S.; Matsunaga, K.; Horn, E.; Furukawa, N.; Nabeshima, T. Isolation and Molecular Structure of the Organo-Persulfuranes [12−S−6(C6)]. J. Am. Chem. Soc. 2006, 128 (21), 6778–6779. https://doi.org/10.1021/ja060497y.






          share|improve this answer














          share|improve this answer



          share|improve this answer








          edited 29 mins ago

























          answered 1 hour ago









          andseliskandselisk

          20.6k669133




          20.6k669133







          • 2




            $begingroup$
            I think OP is looking for something of the form $ce(R4S^2+)(X^-)2$, which isn't quite the same, albeit quite close...
            $endgroup$
            – orthocresol
            1 hour ago







          • 2




            $begingroup$
            @orthocresol I see; it seems like dx.doi.org/10.1021/ja971336k and dx.doi.org/10.1021/ja060497y would make a better answer then; I'm going to edit the more recent work in within the next hour:)
            $endgroup$
            – andselisk
            1 hour ago













          • 2




            $begingroup$
            I think OP is looking for something of the form $ce(R4S^2+)(X^-)2$, which isn't quite the same, albeit quite close...
            $endgroup$
            – orthocresol
            1 hour ago







          • 2




            $begingroup$
            @orthocresol I see; it seems like dx.doi.org/10.1021/ja971336k and dx.doi.org/10.1021/ja060497y would make a better answer then; I'm going to edit the more recent work in within the next hour:)
            $endgroup$
            – andselisk
            1 hour ago








          2




          2




          $begingroup$
          I think OP is looking for something of the form $ce(R4S^2+)(X^-)2$, which isn't quite the same, albeit quite close...
          $endgroup$
          – orthocresol
          1 hour ago





          $begingroup$
          I think OP is looking for something of the form $ce(R4S^2+)(X^-)2$, which isn't quite the same, albeit quite close...
          $endgroup$
          – orthocresol
          1 hour ago





          2




          2




          $begingroup$
          @orthocresol I see; it seems like dx.doi.org/10.1021/ja971336k and dx.doi.org/10.1021/ja060497y would make a better answer then; I'm going to edit the more recent work in within the next hour:)
          $endgroup$
          – andselisk
          1 hour ago





          $begingroup$
          @orthocresol I see; it seems like dx.doi.org/10.1021/ja971336k and dx.doi.org/10.1021/ja060497y would make a better answer then; I'm going to edit the more recent work in within the next hour:)
          $endgroup$
          – andselisk
          1 hour ago


















          draft saved

          draft discarded
















































          Thanks for contributing an answer to Chemistry Stack Exchange!


          • Please be sure to answer the question. Provide details and share your research!

          But avoid


          • Asking for help, clarification, or responding to other answers.

          • Making statements based on opinion; back them up with references or personal experience.

          Use MathJax to format equations. MathJax reference.


          To learn more, see our tips on writing great answers.




          draft saved


          draft discarded














          StackExchange.ready(
          function ()
          StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fchemistry.stackexchange.com%2fquestions%2f114887%2fdo-quaternary-sulfur-dications-exist%23new-answer', 'question_page');

          );

          Post as a guest















          Required, but never shown





















































          Required, but never shown














          Required, but never shown












          Required, but never shown







          Required, but never shown

































          Required, but never shown














          Required, but never shown












          Required, but never shown







          Required, but never shown







          Popular posts from this blog

          Invision Community Contents History See also References External links Navigation menuProprietaryinvisioncommunity.comIPS Community ForumsIPS Community Forumsthis blog entry"License Changes, IP.Board 3.4, and the Future""Interview -- Matt Mecham of Ibforums""CEO Invision Power Board, Matt Mecham Is a Liar, Thief!"IPB License Explanation 1.3, 1.3.1, 2.0, and 2.1ArchivedSecurity Fixes, Updates And Enhancements For IPB 1.3.1Archived"New Demo Accounts - Invision Power Services"the original"New Default Skin"the original"Invision Power Board 3.0.0 and Applications Released"the original"Archived copy"the original"Perpetual licenses being done away with""Release Notes - Invision Power Services""Introducing: IPS Community Suite 4!"Invision Community Release Notes

          Canceling a color specificationRandomly assigning color to Graphics3D objects?Default color for Filling in Mathematica 9Coloring specific elements of sets with a prime modified order in an array plotHow to pick a color differing significantly from the colors already in a given color list?Detection of the text colorColor numbers based on their valueCan color schemes for use with ColorData include opacity specification?My dynamic color schemes

          Tom Holland Mục lục Đầu đời và giáo dục | Sự nghiệp | Cuộc sống cá nhân | Phim tham gia | Giải thưởng và đề cử | Chú thích | Liên kết ngoài | Trình đơn chuyển hướngProfile“Person Details for Thomas Stanley Holland, "England and Wales Birth Registration Index, 1837-2008" — FamilySearch.org”"Meet Tom Holland... the 16-year-old star of The Impossible""Schoolboy actor Tom Holland finds himself in Oscar contention for role in tsunami drama"“Naomi Watts on the Prince William and Harry's reaction to her film about the late Princess Diana”lưu trữ"Holland and Pflueger Are West End's Two New 'Billy Elliots'""I'm so envious of my son, the movie star! British writer Dominic Holland's spent 20 years trying to crack Hollywood - but he's been beaten to it by a very unlikely rival"“Richard and Margaret Povey of Jersey, Channel Islands, UK: Information about Thomas Stanley Holland”"Tom Holland to play Billy Elliot""New Billy Elliot leaving the garage"Billy Elliot the Musical - Tom Holland - Billy"A Tale of four Billys: Tom Holland""The Feel Good Factor""Thames Christian College schoolboys join Myleene Klass for The Feelgood Factor""Government launches £600,000 arts bursaries pilot""BILLY's Chapman, Holland, Gardner & Jackson-Keen Visit Prime Minister""Elton John 'blown away' by Billy Elliot fifth birthday" (video with John's interview and fragments of Holland's performance)"First News interviews Arrietty's Tom Holland"“33rd Critics' Circle Film Awards winners”“National Board of Review Current Awards”Bản gốc"Ron Howard Whaling Tale 'In The Heart Of The Sea' Casts Tom Holland"“'Spider-Man' Finds Tom Holland to Star as New Web-Slinger”lưu trữ“Captain America: Civil War (2016)”“Film Review: ‘Captain America: Civil War’”lưu trữ“‘Captain America: Civil War’ review: Choose your own avenger”lưu trữ“The Lost City of Z reviews”“Sony Pictures and Marvel Studios Find Their 'Spider-Man' Star and Director”“‘Mary Magdalene’, ‘Current War’ & ‘Wind River’ Get 2017 Release Dates From Weinstein”“Lionsgate Unleashing Daisy Ridley & Tom Holland Starrer ‘Chaos Walking’ In Cannes”“PTA's 'Master' Leads Chicago Film Critics Nominations, UPDATED: Houston and Indiana Critics Nominations”“Nominaciones Goya 2013 Telecinco Cinema – ENG”“Jameson Empire Film Awards: Martin Freeman wins best actor for performance in The Hobbit”“34th Annual Young Artist Awards”Bản gốc“Teen Choice Awards 2016—Captain America: Civil War Leads Second Wave of Nominations”“BAFTA Film Award Nominations: ‘La La Land’ Leads Race”“Saturn Awards Nominations 2017: 'Rogue One,' 'Walking Dead' Lead”Tom HollandTom HollandTom HollandTom Hollandmedia.gettyimages.comWorldCat Identities300279794no20130442900000 0004 0355 42791085670554170004732cb16706349t(data)XX5557367