Trivalent Actinide Ions Showing Tenfold Coordination in Solution
Trivalent actinides generally exhibit ninefold coordination in solution. 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPr-BTP), a tridentate nitrogen donor ligand, is known to form ninefold coordinated 1:3 complexes, [An(nPr-BTP)3]3+ (An = U, Pu, Am, Cm) in solution. We report a Cm(III) complex...
Gespeichert in:
| Hauptverfasser: | , , , , , , , , , |
|---|---|
| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
14 August 2020
|
| In: |
Inorganic chemistry
Year: 2020, Jahrgang: 59, Heft: 17, Pages: 12410-12421 |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.0c01526 |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.inorgchem.0c01526
|
| Verfasserangaben: | Patrik Weßling, Tobias Schenk, Felix Braun, Björn B. Beele, Sascha Trumm, Michael Trumm, Bernd Schimmelpfennig, Dieter Schild, Andreas Geist, and Petra J. Panak |
MARC
| LEADER | 00000caa a2200000 c 4500 | ||
|---|---|---|---|
| 001 | 1735631116 | ||
| 003 | DE-627 | ||
| 005 | 20220818225324.0 | ||
| 007 | cr uuu---uuuuu | ||
| 008 | 201015s2020 xx |||||o 00| ||eng c | ||
| 024 | 7 | |a 10.1021/acs.inorgchem.0c01526 |2 doi | |
| 035 | |a (DE-627)1735631116 | ||
| 035 | |a (DE-599)KXP1735631116 | ||
| 035 | |a (OCoLC)1341371227 | ||
| 040 | |a DE-627 |b ger |c DE-627 |e rda | ||
| 041 | |a eng | ||
| 084 | |a 30 |2 sdnb | ||
| 100 | 1 | |a Weßling, Patrik |d 1992- |e VerfasserIn |0 (DE-588)1201055911 |0 (DE-627)1684202809 |4 aut | |
| 245 | 1 | 0 | |a Trivalent Actinide Ions Showing Tenfold Coordination in Solution |c Patrik Weßling, Tobias Schenk, Felix Braun, Björn B. Beele, Sascha Trumm, Michael Trumm, Bernd Schimmelpfennig, Dieter Schild, Andreas Geist, and Petra J. Panak |
| 264 | 1 | |c 14 August 2020 | |
| 300 | |a 12 | ||
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a Computermedien |b c |2 rdamedia | ||
| 338 | |a Online-Ressource |b cr |2 rdacarrier | ||
| 500 | |a Gesehen am 15.10.2020 | ||
| 520 | |a Trivalent actinides generally exhibit ninefold coordination in solution. 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPr-BTP), a tridentate nitrogen donor ligand, is known to form ninefold coordinated 1:3 complexes, [An(nPr-BTP)3]3+ (An = U, Pu, Am, Cm) in solution. We report a Cm(III) complex with tenfold coordination in solution, [Cm(nPr-BTP)3(NO3)]2+. This species was identified using time-resolved laser fluorescence spectroscopy (TRLFS), vibronic side band spectroscopy (VSBS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). Adding nitrate to a solution of the [Cm(nPr-BTP)3]3+ complex in 2-propanol shifts the Cm(III) emission band from 613.1 to 617.3 nm. This bathochromic shift is due to a higher coordination number of the Cm(III) ion in solution, in agreement with the formation of the [Cm(nPr-BTP)3(NO3)]2+ complex. The formation of this complex exhibits slow kinetics in the range of 5 to 12 days, depending on the water content of the solvent. Formation of a complex [Cm(nPr-BTP)3(X)]2+ was not observed for anions other than nitrate (X- = NO2-, CN-, or OTf-). The formation of the [Cm(nPr-BTP)3(NO3)]2+ complex was studied as a function of NO3- and nPr-BTP concentrations, and slope analyses confirmed the addition of one nitrate anion to the [Cm(nPr-BTP)3]3+ complex. Experiments with varied nPr-BTP concentration show that [Cm(nPr-BTP)3(NO3)]2+ only forms at nPr-BTP concentrations below 10-4 mol/L whereas for concentrations greater than 10-4 mol/L the formation of the tenfold species is suppressed and [Cm(nPr-BTP)3]3+ is the only species present. The presence of the tenfold coordinated complex is supported by VSBS, XPS, and DFT calculations. The vibronic side band of the [Cm(nPr-BTP)3(NO3)]2+ complex exhibits a nitrate stretching mode not observed in the [Cm(nPr-BTP)3]3+ complex. Moreover, XPS on [M(nPr-BTP)3(NO3)](NO3)2 (M = Eu, Am) yields signals from both non-coordinated and coordinated nitrate. Finally, DFT calculations reveal that the energetically most favored structure is obtained if the nitrate is positioned on the C2 axis of the D3 symmetrical [Cm(nPr-BTP)3]3+ complex with a bond distance of 413 pm. Combining results from TRLFS, VSBS, XPS, and DFT provides sound evidence for a unique tenfold coordinated Cm(III) complex in solution—a novelty in An(III) solution chemistry. | ||
| 700 | 1 | |a Schenk, Tobias |e VerfasserIn |4 aut | |
| 700 | 1 | |a Braun, Felix |d 1990- |e VerfasserIn |0 (DE-588)121289197X |0 (DE-627)1702964191 |4 aut | |
| 700 | 1 | |a Beele, Björn B. |e VerfasserIn |0 (DE-588)139654054 |0 (DE-627)703416804 |0 (DE-576)31260761X |4 aut | |
| 700 | 1 | |a Trumm, Sascha |e VerfasserIn |0 (DE-588)140989935 |0 (DE-627)623812614 |0 (DE-576)32168530X |4 aut | |
| 700 | 1 | |a Trumm, Michael |e VerfasserIn |0 (DE-588)1019604360 |0 (DE-627)690963998 |0 (DE-576)358417589 |4 aut | |
| 700 | 1 | |a Schimmelpfennig, Bernd |e VerfasserIn |4 aut | |
| 700 | 1 | |a Schild, Dieter |e VerfasserIn |4 aut | |
| 700 | 1 | |a Geist, Andreas |e VerfasserIn |0 (DE-588)1161861556 |0 (DE-627)102538234X |0 (DE-576)506942112 |4 aut | |
| 700 | 1 | |a Panak, Petra |e VerfasserIn |0 (DE-588)1084656000 |0 (DE-627)848640217 |0 (DE-576)456626727 |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Inorganic chemistry |d Washington, DC : American Chemical Society, 1962 |g 59(2020), 17, Seite 12410-12421 |h Online-Ressource |w (DE-627)301510911 |w (DE-600)1484438-2 |w (DE-576)090854942 |x 1520-510X |7 nnas |a Trivalent Actinide Ions Showing Tenfold Coordination in Solution |
| 773 | 1 | 8 | |g volume:59 |g year:2020 |g number:17 |g pages:12410-12421 |g extent:12 |a Trivalent Actinide Ions Showing Tenfold Coordination in Solution |
| 856 | 4 | 0 | |u https://doi.org/10.1021/acs.inorgchem.0c01526 |x Verlag |x Resolving-System |z lizenzpflichtig |3 Volltext |
| 951 | |a AR | ||
| 992 | |a 20201015 | ||
| 993 | |a Article | ||
| 994 | |a 2020 | ||
| 998 | |g 1084656000 |a Panak, Petra |m 1084656000:Panak, Petra |d 120000 |d 120300 |e 120000PP1084656000 |e 120300PP1084656000 |k 0/120000/ |k 1/120000/120300/ |p 10 |y j | ||
| 998 | |g 121289197X |a Braun, Felix |m 121289197X:Braun, Felix |d 120000 |e 120000PB121289197X |k 0/120000/ |p 3 | ||
| 998 | |g 1201055911 |a Weßling, Patrik |m 1201055911:Weßling, Patrik |d 120000 |d 120300 |e 120000PW1201055911 |e 120300PW1201055911 |k 0/120000/ |k 1/120000/120300/ |p 1 |x j | ||
| 999 | |a KXP-PPN1735631116 |e 3780075660 | ||
| BIB | |a Y | ||
| SER | |a journal | ||
| JSO | |a {"type":{"bibl":"article-journal","media":"Online-Ressource"},"id":{"eki":["1735631116"],"doi":["10.1021/acs.inorgchem.0c01526"]},"name":{"displayForm":["Patrik Weßling, Tobias Schenk, Felix Braun, Björn B. Beele, Sascha Trumm, Michael Trumm, Bernd Schimmelpfennig, Dieter Schild, Andreas Geist, and Petra J. Panak"]},"note":["Gesehen am 15.10.2020"],"physDesc":[{"extent":"12 S."}],"person":[{"roleDisplay":"VerfasserIn","given":"Patrik","family":"Weßling","role":"aut","display":"Weßling, Patrik"},{"display":"Schenk, Tobias","role":"aut","given":"Tobias","family":"Schenk","roleDisplay":"VerfasserIn"},{"roleDisplay":"VerfasserIn","family":"Braun","given":"Felix","role":"aut","display":"Braun, Felix"},{"given":"Björn B.","family":"Beele","roleDisplay":"VerfasserIn","display":"Beele, Björn B.","role":"aut"},{"family":"Trumm","given":"Sascha","roleDisplay":"VerfasserIn","display":"Trumm, Sascha","role":"aut"},{"given":"Michael","family":"Trumm","roleDisplay":"VerfasserIn","display":"Trumm, Michael","role":"aut"},{"roleDisplay":"VerfasserIn","family":"Schimmelpfennig","given":"Bernd","role":"aut","display":"Schimmelpfennig, Bernd"},{"display":"Schild, Dieter","role":"aut","given":"Dieter","family":"Schild","roleDisplay":"VerfasserIn"},{"display":"Geist, Andreas","role":"aut","given":"Andreas","family":"Geist","roleDisplay":"VerfasserIn"},{"display":"Panak, Petra","role":"aut","family":"Panak","given":"Petra","roleDisplay":"VerfasserIn"}],"title":[{"title_sort":"Trivalent Actinide Ions Showing Tenfold Coordination in Solution","title":"Trivalent Actinide Ions Showing Tenfold Coordination in Solution"}],"recId":"1735631116","relHost":[{"physDesc":[{"extent":"Online-Ressource"}],"language":["eng"],"origin":[{"publisherPlace":"Washington, DC","publisher":"American Chemical Society","dateIssuedDisp":"1962-","dateIssuedKey":"1962"}],"recId":"301510911","title":[{"title_sort":"Inorganic chemistry","title":"Inorganic chemistry"}],"pubHistory":["1.1962 -"],"disp":"Trivalent Actinide Ions Showing Tenfold Coordination in SolutionInorganic chemistry","part":{"pages":"12410-12421","text":"59(2020), 17, Seite 12410-12421","volume":"59","year":"2020","extent":"12","issue":"17"},"type":{"media":"Online-Ressource","bibl":"periodical"},"id":{"zdb":["1484438-2"],"issn":["1520-510X"],"eki":["301510911"]},"name":{"displayForm":["American Chemical Society"]},"corporate":[{"roleDisplay":"Herausgebendes Organ","display":"American Chemical Society","role":"isb"}],"note":["Gesehen am 22.03.23"]}],"language":["eng"],"origin":[{"dateIssuedKey":"2020","dateIssuedDisp":"14 August 2020"}]} | ||
| SRT | |a WESSLINGPATRIVALENTA1420 | ||