The Homopolyatomic Sulfur Cation [S<sub>20</sub>]<sup>2+</sup>
Homopolyatomic cations of the main group elements and of the element sulfur, in particular, are used as tutorial examples to teach structure and bonding in inorganic chemistry. So far, the cations [S<sub>4</sub>]<sup>2+</sup>, [S<sub>8</sub>]<sup>2+</sup&...
Saved in:
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-01-01
|
| Series: | Inorganics |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2304-6740/13/1/23 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1832588290103967744 |
|---|---|
| author | Janis Derendorf Lara Heiderich Carsten Jenne Marc C. Nierstenhöfer |
| author_facet | Janis Derendorf Lara Heiderich Carsten Jenne Marc C. Nierstenhöfer |
| author_sort | Janis Derendorf |
| collection | DOAJ |
| description | Homopolyatomic cations of the main group elements and of the element sulfur, in particular, are used as tutorial examples to teach structure and bonding in inorganic chemistry. So far, the cations [S<sub>4</sub>]<sup>2+</sup>, [S<sub>8</sub>]<sup>2+</sup>, [S<sub>19</sub>]<sup>2+</sup>, [S<sub>5</sub>]<sup>•+</sup>, and [S<sub>8</sub>]<sup>•+</sup> are known experimentally. In this report, the generation and crystal structure determination of the salt Na<sub>2</sub>[S<sub>20</sub>]<sub>2</sub>[B<sub>12</sub>Cl<sub>12</sub>]<sub>3</sub>, containing the new homopolyatomic sulfur cation [S<sub>20</sub>]<sup>2+</sup>, is reported. The structure of the latter cation consists of two seven-membered homocycles, which are bridged by a six-membered sulfur chain. This structure is strongly related to that of [S<sub>19</sub>]<sup>2+</sup>. The heptasulfur rings show pronounced bond alternation. Comparison with the experimental structures of [S<sub>7</sub>X]<sup>+</sup> (X = I, Br) and the application of quantum chemical calculations show unambiguously that the observed structural features are intrinsic properties of the cationic <i>cyclo</i>-heptasulfur moieties. The latter can occupy different conformations, which only slightly differ in energy. Charge delocalization and negative hyperconjugation contribute to the stability of the observed structures. The discovery of the [S<sub>20</sub>]<sup>2+</sup> cation fits well into range of known homopolyatomic sulfur cations, which can be classified by their averaged oxidation state of sulfur. |
| format | Article |
| id | doaj-art-97dd937de80648d6867fb74bd5e85cbb |
| institution | Kabale University |
| issn | 2304-6740 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj-art-97dd937de80648d6867fb74bd5e85cbb2025-01-24T13:35:31ZengMDPI AGInorganics2304-67402025-01-011312310.3390/inorganics13010023The Homopolyatomic Sulfur Cation [S<sub>20</sub>]<sup>2+</sup>Janis Derendorf0Lara Heiderich1Carsten Jenne2Marc C. Nierstenhöfer3Anorganische Chemie, Fakultät für Mathematik und Naturwissenschaften, Bergische Universität Wuppertal, Gaußstr. 20, 42119 Wuppertal, GermanyAnorganische Chemie, Fakultät für Mathematik und Naturwissenschaften, Bergische Universität Wuppertal, Gaußstr. 20, 42119 Wuppertal, GermanyAnorganische Chemie, Fakultät für Mathematik und Naturwissenschaften, Bergische Universität Wuppertal, Gaußstr. 20, 42119 Wuppertal, GermanyAnorganische Chemie, Fakultät für Mathematik und Naturwissenschaften, Bergische Universität Wuppertal, Gaußstr. 20, 42119 Wuppertal, GermanyHomopolyatomic cations of the main group elements and of the element sulfur, in particular, are used as tutorial examples to teach structure and bonding in inorganic chemistry. So far, the cations [S<sub>4</sub>]<sup>2+</sup>, [S<sub>8</sub>]<sup>2+</sup>, [S<sub>19</sub>]<sup>2+</sup>, [S<sub>5</sub>]<sup>•+</sup>, and [S<sub>8</sub>]<sup>•+</sup> are known experimentally. In this report, the generation and crystal structure determination of the salt Na<sub>2</sub>[S<sub>20</sub>]<sub>2</sub>[B<sub>12</sub>Cl<sub>12</sub>]<sub>3</sub>, containing the new homopolyatomic sulfur cation [S<sub>20</sub>]<sup>2+</sup>, is reported. The structure of the latter cation consists of two seven-membered homocycles, which are bridged by a six-membered sulfur chain. This structure is strongly related to that of [S<sub>19</sub>]<sup>2+</sup>. The heptasulfur rings show pronounced bond alternation. Comparison with the experimental structures of [S<sub>7</sub>X]<sup>+</sup> (X = I, Br) and the application of quantum chemical calculations show unambiguously that the observed structural features are intrinsic properties of the cationic <i>cyclo</i>-heptasulfur moieties. The latter can occupy different conformations, which only slightly differ in energy. Charge delocalization and negative hyperconjugation contribute to the stability of the observed structures. The discovery of the [S<sub>20</sub>]<sup>2+</sup> cation fits well into range of known homopolyatomic sulfur cations, which can be classified by their averaged oxidation state of sulfur.https://www.mdpi.com/2304-6740/13/1/23crystal structures<i>closo</i>-dodecaborates<i>cyclo</i>-heptasulfurhomopolyatomic cationsnon-metal cationssulfur |
| spellingShingle | Janis Derendorf Lara Heiderich Carsten Jenne Marc C. Nierstenhöfer The Homopolyatomic Sulfur Cation [S<sub>20</sub>]<sup>2+</sup> Inorganics crystal structures <i>closo</i>-dodecaborates <i>cyclo</i>-heptasulfur homopolyatomic cations non-metal cations sulfur |
| title | The Homopolyatomic Sulfur Cation [S<sub>20</sub>]<sup>2+</sup> |
| title_full | The Homopolyatomic Sulfur Cation [S<sub>20</sub>]<sup>2+</sup> |
| title_fullStr | The Homopolyatomic Sulfur Cation [S<sub>20</sub>]<sup>2+</sup> |
| title_full_unstemmed | The Homopolyatomic Sulfur Cation [S<sub>20</sub>]<sup>2+</sup> |
| title_short | The Homopolyatomic Sulfur Cation [S<sub>20</sub>]<sup>2+</sup> |
| title_sort | homopolyatomic sulfur cation s sub 20 sub sup 2 sup |
| topic | crystal structures <i>closo</i>-dodecaborates <i>cyclo</i>-heptasulfur homopolyatomic cations non-metal cations sulfur |
| url | https://www.mdpi.com/2304-6740/13/1/23 |
| work_keys_str_mv | AT janisderendorf thehomopolyatomicsulfurcationssub20subsup2sup AT laraheiderich thehomopolyatomicsulfurcationssub20subsup2sup AT carstenjenne thehomopolyatomicsulfurcationssub20subsup2sup AT marccnierstenhofer thehomopolyatomicsulfurcationssub20subsup2sup AT janisderendorf homopolyatomicsulfurcationssub20subsup2sup AT laraheiderich homopolyatomicsulfurcationssub20subsup2sup AT carstenjenne homopolyatomicsulfurcationssub20subsup2sup AT marccnierstenhofer homopolyatomicsulfurcationssub20subsup2sup |