Organotin(IV) trifluoromethanesulfonate chemistry: isolation and characterization of novel 1,10-phenanthroline-based derivatives
The reactivity of the hydroxo di-n-butyltin trifluoromethanesulfonato dimer complex [n-Bu2Sn(µ-OH)(H2O)(CF3SO3)]2 (1) toward 1,10-phenanthroline (phen) has been investigated, leading to the formation of two novel di-n-butyltin(IV) trifluoromethanesulfonate complexes [n-Bu2Sn(µ-OH)(phen)]2[CF3SO3]2 (...
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Académie des sciences
2024-05-01
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| Series: | Comptes Rendus. Chimie |
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| Online Access: | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.260/ |
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| author | Cattey, Hélène Plasseraud, Laurent |
| author_facet | Cattey, Hélène Plasseraud, Laurent |
| author_sort | Cattey, Hélène |
| collection | DOAJ |
| description | The reactivity of the hydroxo di-n-butyltin trifluoromethanesulfonato dimer complex [n-Bu2Sn(µ-OH)(H2O)(CF3SO3)]2 (1) toward 1,10-phenanthroline (phen) has been investigated, leading to the formation of two novel di-n-butyltin(IV) trifluoromethanesulfonate complexes [n-Bu2Sn(µ-OH)(phen)]2[CF3SO3]2 (5) and [n-Bu2Sn(phen)2][CF3SO3]2 (6), in which the tin atoms are bis-chelated by one and two bidentate phen ligands, respectively. Salts 5 and 6 were characterized by single crystal X-ray diffraction analysis, elemental analysis, mass spectrometry, and infrared spectroscopy as well as 1H, 19F, 13C{1H}, and 119Sn{1H} NMR spectroscopy. Monitoring by 119Sn{1H} NMR spectroscopy in CD3CN solution of the reaction proceeding with successive addition of phen revealed the in situ formation of three organotin(IV) trifluoromethanesulfonate intermediate species. Two of these, namely {[n-Bu2Sn(H2O)]2O·n-Bu2Sn(OH)2}[CF3SO3]2 (2) and [n-Bu2Sn2(OH)(CF3SO3)]2O (4), were already known and could be clearly identified on the basis of their 119Sn{119H} NMR chemical shifts. The composition of the third intermediate, 3, with an unknown chemical shift value, was investigated. A possible structure, especially suggested by electrospray-ionization mass spectrometry, is proposed as [{n-Bu2Sn(phen)(CF3SO3)}2(µ-CF3SO3)][CF3SO3]. Furthermore, from a mixture of 1 and phen in equimolar ratio, in dichloromethane solvent and at –20 °C, temperature-sensitive crystals of a new hydrated di-n-butyltin cation, [n-Bu2Sn(phen)(OH)(H2O)][CF3SO3] (7), were isolated. Crystals of the organic salt 1,10-phenanthrolinium trifluoromethanesulfonate (phenHOTf) were also obtained from the filtrate of the mother-liquor. The reactivity of 1 toward 2,9-dimethyl-1,10-phenanthroline was also explored (dmphen), leading to the detection of characteristic fingerprints of distannoxanes 2 and 4 by 119Sn{119H} NMR, and to the crystallization of phenanthrolinium triflate salts, which were characterized by X-ray diffraction analysis as dmphenHOTf and dmphenHOTf·dmphen. |
| format | Article |
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| institution | Kabale University |
| issn | 1878-1543 |
| language | English |
| publishDate | 2024-05-01 |
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| spelling | doaj-art-62e99dc2e50743a49f17fc8514ca08622025-02-07T13:39:09ZengAcadémie des sciencesComptes Rendus. Chimie1878-15432024-05-0127S1173410.5802/crchim.26010.5802/crchim.260Organotin(IV) trifluoromethanesulfonate chemistry: isolation and characterization of novel 1,10-phenanthroline-based derivativesCattey, Hélène0https://orcid.org/0000-0002-4416-7510Plasseraud, Laurent1https://orcid.org/0000-0002-7870-1881Institut de Chimie Moléculaire de l’Université de Bourgogne, UMR-CNRS 6302, Université de Bourgogne, 9 avenue A. Savary, F-21078 Dijon, FranceInstitut de Chimie Moléculaire de l’Université de Bourgogne, UMR-CNRS 6302, Université de Bourgogne, 9 avenue A. Savary, F-21078 Dijon, FranceThe reactivity of the hydroxo di-n-butyltin trifluoromethanesulfonato dimer complex [n-Bu2Sn(µ-OH)(H2O)(CF3SO3)]2 (1) toward 1,10-phenanthroline (phen) has been investigated, leading to the formation of two novel di-n-butyltin(IV) trifluoromethanesulfonate complexes [n-Bu2Sn(µ-OH)(phen)]2[CF3SO3]2 (5) and [n-Bu2Sn(phen)2][CF3SO3]2 (6), in which the tin atoms are bis-chelated by one and two bidentate phen ligands, respectively. Salts 5 and 6 were characterized by single crystal X-ray diffraction analysis, elemental analysis, mass spectrometry, and infrared spectroscopy as well as 1H, 19F, 13C{1H}, and 119Sn{1H} NMR spectroscopy. Monitoring by 119Sn{1H} NMR spectroscopy in CD3CN solution of the reaction proceeding with successive addition of phen revealed the in situ formation of three organotin(IV) trifluoromethanesulfonate intermediate species. Two of these, namely {[n-Bu2Sn(H2O)]2O·n-Bu2Sn(OH)2}[CF3SO3]2 (2) and [n-Bu2Sn2(OH)(CF3SO3)]2O (4), were already known and could be clearly identified on the basis of their 119Sn{119H} NMR chemical shifts. The composition of the third intermediate, 3, with an unknown chemical shift value, was investigated. A possible structure, especially suggested by electrospray-ionization mass spectrometry, is proposed as [{n-Bu2Sn(phen)(CF3SO3)}2(µ-CF3SO3)][CF3SO3]. Furthermore, from a mixture of 1 and phen in equimolar ratio, in dichloromethane solvent and at –20 °C, temperature-sensitive crystals of a new hydrated di-n-butyltin cation, [n-Bu2Sn(phen)(OH)(H2O)][CF3SO3] (7), were isolated. Crystals of the organic salt 1,10-phenanthrolinium trifluoromethanesulfonate (phenHOTf) were also obtained from the filtrate of the mother-liquor. The reactivity of 1 toward 2,9-dimethyl-1,10-phenanthroline was also explored (dmphen), leading to the detection of characteristic fingerprints of distannoxanes 2 and 4 by 119Sn{119H} NMR, and to the crystallization of phenanthrolinium triflate salts, which were characterized by X-ray diffraction analysis as dmphenHOTf and dmphenHOTf·dmphen.https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.260/Di-<i>n</i>-butyltin(IV) complexesTrifluoromethanesulfonate anionNitrogen-containing heterocyclic compounds1,10-Phenanthroline derivatives<sup>119</sup>Sn{<sup>1</sup>H} NMR monitoringSingle crystal X-ray diffraction |
| spellingShingle | Cattey, Hélène Plasseraud, Laurent Organotin(IV) trifluoromethanesulfonate chemistry: isolation and characterization of novel 1,10-phenanthroline-based derivatives Comptes Rendus. Chimie Di-<i>n</i>-butyltin(IV) complexes Trifluoromethanesulfonate anion Nitrogen-containing heterocyclic compounds 1,10-Phenanthroline derivatives <sup>119</sup>Sn{<sup>1</sup>H} NMR monitoring Single crystal X-ray diffraction |
| title | Organotin(IV) trifluoromethanesulfonate chemistry: isolation and characterization of novel 1,10-phenanthroline-based derivatives |
| title_full | Organotin(IV) trifluoromethanesulfonate chemistry: isolation and characterization of novel 1,10-phenanthroline-based derivatives |
| title_fullStr | Organotin(IV) trifluoromethanesulfonate chemistry: isolation and characterization of novel 1,10-phenanthroline-based derivatives |
| title_full_unstemmed | Organotin(IV) trifluoromethanesulfonate chemistry: isolation and characterization of novel 1,10-phenanthroline-based derivatives |
| title_short | Organotin(IV) trifluoromethanesulfonate chemistry: isolation and characterization of novel 1,10-phenanthroline-based derivatives |
| title_sort | organotin iv trifluoromethanesulfonate chemistry isolation and characterization of novel 1 10 phenanthroline based derivatives |
| topic | Di-<i>n</i>-butyltin(IV) complexes Trifluoromethanesulfonate anion Nitrogen-containing heterocyclic compounds 1,10-Phenanthroline derivatives <sup>119</sup>Sn{<sup>1</sup>H} NMR monitoring Single crystal X-ray diffraction |
| url | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.260/ |
| work_keys_str_mv | AT catteyhelene organotinivtrifluoromethanesulfonatechemistryisolationandcharacterizationofnovel110phenanthrolinebasedderivatives AT plasseraudlaurent organotinivtrifluoromethanesulfonatechemistryisolationandcharacterizationofnovel110phenanthrolinebasedderivatives |