Do quaternary sulfur dications exist?Why doesn't H₄O²⁺ 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?

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Do quaternary sulfur dications exist?


Why doesn't H₄O²⁺ 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?













7












$begingroup$


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











$endgroup$











  • $begingroup$
    chemistry.stackexchange.com/questions/112087/…
    $endgroup$
    – Mithoron
    May 7 at 0:36















7












$begingroup$


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











$endgroup$











  • $begingroup$
    chemistry.stackexchange.com/questions/112087/…
    $endgroup$
    – Mithoron
    May 7 at 0:36













7












7








7


1



$begingroup$


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 May 6 at 1:49









orthocresol

41.2k7123254




41.2k7123254










asked May 6 at 1:02









user73910user73910

1424




1424











  • $begingroup$
    chemistry.stackexchange.com/questions/112087/…
    $endgroup$
    – Mithoron
    May 7 at 0:36
















  • $begingroup$
    chemistry.stackexchange.com/questions/112087/…
    $endgroup$
    – Mithoron
    May 7 at 0:36















$begingroup$
chemistry.stackexchange.com/questions/112087/…
$endgroup$
– Mithoron
May 7 at 0:36




$begingroup$
chemistry.stackexchange.com/questions/112087/…
$endgroup$
– Mithoron
May 7 at 0:36










1 Answer
1






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10












$begingroup$

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.





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    $begingroup$

    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











    $endgroup$

















      10












      $begingroup$

      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











      $endgroup$















        10












        10








        10





        $begingroup$

        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 May 6 at 2:35

























        answered May 6 at 1:35









        andseliskandselisk

        21.3k772138




        21.3k772138



























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