Effect of the Positioning of Metal Centers on a Cavitand in the Ruthenium-Catalyzed <i>N</i>-Alkylation of Amines
Two bis-ruthenium(II) complexes, namely <i>N</i>,<i>N′</i>-{5,17-diamino-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene}-bis-[dichloro-(<i>p</i>-cymene)-ruthenium(II)] (<b>1</b>) and <i>N</i>,<i>N′...
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2025-02-01
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| author | Neslihan Şahin Christophe Gourlaouen David Sémeril |
| author_facet | Neslihan Şahin Christophe Gourlaouen David Sémeril |
| author_sort | Neslihan Şahin |
| collection | DOAJ |
| description | Two bis-ruthenium(II) complexes, namely <i>N</i>,<i>N′</i>-{5,17-diamino-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene}-bis-[dichloro-(<i>p</i>-cymene)-ruthenium(II)] (<b>1</b>) and <i>N</i>,<i>N′</i>-{5,11-diamino-4(24),6(10),12(16), 18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene}-bis-[dichloro-(<i>p</i>-cymene)-ruthenium(II)] (<b>2</b>) were synthesized and tested as catalysts in the <i>N</i>-alkylation of primary amines with arylmethyl alcohol using the green “hydrogen borrowing” methodology. The catalytic results were compared with those obtained when the <i>N</i>-{5-amino-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentyl-resorcin[4]arene}-[dichloro-(<i>p</i>-cymene)-ruthenium(II)] (<b>3</b>) complex was employed as catalyst. The rate of the <i>N</i>-alkylation of aniline with benzyl alcohol increased in the order <b>3</b> < <b>1</b> ≪ <b>2</b>, which highlights the importance of the relative positioning of the two metal centers on the upper rim of the resorcin[4]arene. Theoretical investigations suggest that the grafting of the two “RuCl<sub>2</sub>(<i>p</i>-cymene)NH<sub>2</sub>” moieties on two distal aromatic rings of the cavitand allows a cooperative effect between a ruthenium atom and the coordinated amine of the second metal center. |
| format | Article |
| id | doaj-art-3e63711bd6c04e809e41c0851a2f7050 |
| institution | DOAJ |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj-art-3e63711bd6c04e809e41c0851a2f70502025-08-20T03:12:22ZengMDPI AGMolecules1420-30492025-02-0130495110.3390/molecules30040951Effect of the Positioning of Metal Centers on a Cavitand in the Ruthenium-Catalyzed <i>N</i>-Alkylation of AminesNeslihan Şahin0Christophe Gourlaouen1David Sémeril2Department of Science Education, Faculty of Education, Cumhuriyet University, Sivas 58040, TürkiyeLaboratoire de Modélisation et Simulations Moléculaires, UMR-CNRS 7140, Strasbourg University, 67008 Strasbourg, FranceSynthèse Organométallique et Catalyse, UMR-CNRS 7177, Strasbourg University, 67008 Strasbourg, FranceTwo bis-ruthenium(II) complexes, namely <i>N</i>,<i>N′</i>-{5,17-diamino-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene}-bis-[dichloro-(<i>p</i>-cymene)-ruthenium(II)] (<b>1</b>) and <i>N</i>,<i>N′</i>-{5,11-diamino-4(24),6(10),12(16), 18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene}-bis-[dichloro-(<i>p</i>-cymene)-ruthenium(II)] (<b>2</b>) were synthesized and tested as catalysts in the <i>N</i>-alkylation of primary amines with arylmethyl alcohol using the green “hydrogen borrowing” methodology. The catalytic results were compared with those obtained when the <i>N</i>-{5-amino-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentyl-resorcin[4]arene}-[dichloro-(<i>p</i>-cymene)-ruthenium(II)] (<b>3</b>) complex was employed as catalyst. The rate of the <i>N</i>-alkylation of aniline with benzyl alcohol increased in the order <b>3</b> < <b>1</b> ≪ <b>2</b>, which highlights the importance of the relative positioning of the two metal centers on the upper rim of the resorcin[4]arene. Theoretical investigations suggest that the grafting of the two “RuCl<sub>2</sub>(<i>p</i>-cymene)NH<sub>2</sub>” moieties on two distal aromatic rings of the cavitand allows a cooperative effect between a ruthenium atom and the coordinated amine of the second metal center.https://www.mdpi.com/1420-3049/30/4/951rutheniumresorcin[4]arenecavitandhydrogen borrowingcooperative effectmechanistic computation |
| spellingShingle | Neslihan Şahin Christophe Gourlaouen David Sémeril Effect of the Positioning of Metal Centers on a Cavitand in the Ruthenium-Catalyzed <i>N</i>-Alkylation of Amines Molecules ruthenium resorcin[4]arene cavitand hydrogen borrowing cooperative effect mechanistic computation |
| title | Effect of the Positioning of Metal Centers on a Cavitand in the Ruthenium-Catalyzed <i>N</i>-Alkylation of Amines |
| title_full | Effect of the Positioning of Metal Centers on a Cavitand in the Ruthenium-Catalyzed <i>N</i>-Alkylation of Amines |
| title_fullStr | Effect of the Positioning of Metal Centers on a Cavitand in the Ruthenium-Catalyzed <i>N</i>-Alkylation of Amines |
| title_full_unstemmed | Effect of the Positioning of Metal Centers on a Cavitand in the Ruthenium-Catalyzed <i>N</i>-Alkylation of Amines |
| title_short | Effect of the Positioning of Metal Centers on a Cavitand in the Ruthenium-Catalyzed <i>N</i>-Alkylation of Amines |
| title_sort | effect of the positioning of metal centers on a cavitand in the ruthenium catalyzed i n i alkylation of amines |
| topic | ruthenium resorcin[4]arene cavitand hydrogen borrowing cooperative effect mechanistic computation |
| url | https://www.mdpi.com/1420-3049/30/4/951 |
| work_keys_str_mv | AT neslihansahin effectofthepositioningofmetalcentersonacavitandintherutheniumcatalyzedinialkylationofamines AT christophegourlaouen effectofthepositioningofmetalcentersonacavitandintherutheniumcatalyzedinialkylationofamines AT davidsemeril effectofthepositioningofmetalcentersonacavitandintherutheniumcatalyzedinialkylationofamines |