Structural Variations and Molecular Dynamics of Rare-Earth Metal Complexes with the N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Ligand

Hellmann BJ, Venugopal A, Mix A, Neumann B, Stammler H-G, Willner A, Pape T, Hepp A, Mitzell NW (2009)
CHEMISTRY-A EUROPEAN JOURNAL 15(43): 11701-11709.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
Download
Es wurden keine Dateien hochgeladen. Nur Publikationsnachweis!
Autor*in
Hellmann, Benjamin J.; Venugopal, Ajay; Mix, AndreasUniBi; Neumann, Beate; Stammler, Hans-GeorgUniBi; Willner, Alexander; Pape, Tanja; Hepp, Alexander; Mitzell, Norbert W.
Abstract / Bemerkung
The reaction of the donor-functionalised N,N-bis(2-{pyrid-2-yl}-ethyl)hydroxylamine and [LnCp(3)] (Cp=cyclopentadiene) resulted in the formation of bis(cyclopentadienyl) hydroxylaminato rare-earth metal complexes of the general constitution [Ln(C5H5)(2){ON(C2H4-o-Py)(2)}] (Py=pyridyl) with Ln=Lu (1), Y (2), Ho (3), Sm (4), Nd (5), Pr (6), La (7). These compounds were characterised by elemental analysis. mass spectrometry, NMR spectroscopy (for compounds 1, 2, 4 and 7) and single-crystal X-ray diffraction experiments. The complexes exhibit three different aggregation modes and binding motifs in the solid state. The late rare-earth metal atoms 4, to 5 (Lu, Y, Ho and Sm) form monomeric complexes of the formula [Ln(C5H5)(2)-{eta(2)-ON(C2H4-eta(1)-o-Py)(C2H4-o-Py)}] (1-4, respectively), in which one of the pyridyl nitrogen donor atoms is bonded to the metal atom in addition to file side-on coordinating hydroxylaminato unit. The larger Nd3+ and Pr3+ ions ill 5 and 6 make the hydroxylaminato unit capable of dimerising through the oxygen atoms. This leads to the dimeric complexes [(Ln(C5H5)(2){mu-eta(1):eta(2)-ON(C2H4-o-Py)(2)})(2)] without metal-pyridine bonds. Compound 7 exhibits a dimeric coordination mode similar to the complexes 5 and 6, but, in addition, two pyridyl functions coordinate to the lanthanum atoms leading to the [(La(C5H5)(2){ON(C2H4-o-Py)}{mu-eta(1):eta(2)-ON-(C2H4-eta(1-)o-Py)})(2) ] complex. The aggregation trend is directly related to the size of the metal ions. The complexes with coordinative pyridine-nictal bonds show highly dynamic behaviour in solution. The two pyridine nitrogen atoms rapidly change their coordination to the metal atom at ambient temperature. Variable-temperature (VT) NMR experiments showed that this dynamic exchange call be frozen on the NMR timescale.
Stichworte
O ligands; N ligands; lanthanides; hemilability; hydroxylamines; earths; rare
Erscheinungsjahr
2009
Zeitschriftentitel
CHEMISTRY-A EUROPEAN JOURNAL
Band
15
Ausgabe
43
Seite(n)
11701-11709
ISSN
0947-6539
Page URI
https://pub.uni-bielefeld.de/record/1589597

Zitieren

Hellmann BJ, Venugopal A, Mix A, et al. Structural Variations and Molecular Dynamics of Rare-Earth Metal Complexes with the N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Ligand. CHEMISTRY-A EUROPEAN JOURNAL. 2009;15(43):11701-11709.
Hellmann, B. J., Venugopal, A., Mix, A., Neumann, B., Stammler, H. - G., Willner, A., Pape, T., et al. (2009). Structural Variations and Molecular Dynamics of Rare-Earth Metal Complexes with the N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Ligand. CHEMISTRY-A EUROPEAN JOURNAL, 15(43), 11701-11709. https://doi.org/10.1002/chem.200901448
Hellmann, Benjamin J., Venugopal, Ajay, Mix, Andreas, Neumann, Beate, Stammler, Hans-Georg, Willner, Alexander, Pape, Tanja, Hepp, Alexander, and Mitzell, Norbert W. 2009. “Structural Variations and Molecular Dynamics of Rare-Earth Metal Complexes with the N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Ligand”. CHEMISTRY-A EUROPEAN JOURNAL 15 (43): 11701-11709.
Hellmann, B. J., Venugopal, A., Mix, A., Neumann, B., Stammler, H. - G., Willner, A., Pape, T., Hepp, A., and Mitzell, N. W. (2009). Structural Variations and Molecular Dynamics of Rare-Earth Metal Complexes with the N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Ligand. CHEMISTRY-A EUROPEAN JOURNAL 15, 11701-11709.
Hellmann, B.J., et al., 2009. Structural Variations and Molecular Dynamics of Rare-Earth Metal Complexes with the N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Ligand. CHEMISTRY-A EUROPEAN JOURNAL, 15(43), p 11701-11709.
B.J. Hellmann, et al., “Structural Variations and Molecular Dynamics of Rare-Earth Metal Complexes with the N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Ligand”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 15, 2009, pp. 11701-11709.
Hellmann, B.J., Venugopal, A., Mix, A., Neumann, B., Stammler, H.-G., Willner, A., Pape, T., Hepp, A., Mitzell, N.W.: Structural Variations and Molecular Dynamics of Rare-Earth Metal Complexes with the N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Ligand. CHEMISTRY-A EUROPEAN JOURNAL. 15, 11701-11709 (2009).
Hellmann, Benjamin J., Venugopal, Ajay, Mix, Andreas, Neumann, Beate, Stammler, Hans-Georg, Willner, Alexander, Pape, Tanja, Hepp, Alexander, and Mitzell, Norbert W. “Structural Variations and Molecular Dynamics of Rare-Earth Metal Complexes with the N,N-Bis(2-{pyrid-2-yl}ethyl)hydroxylaminato Ligand”. CHEMISTRY-A EUROPEAN JOURNAL 15.43 (2009): 11701-11709.

1 Zitation in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

Trinuclear pyridyl functionalised hydroxylaminato complexes of aluminium, gallium and indium.
Hellmann BJ, Mix A, Neumann B, Stammler HG, Mitzel NW., Dalton Trans 39(30), 2010
PMID: 20577701

52 References

Daten bereitgestellt von Europe PubMed Central.


AUTHOR UNKNOWN, 0
Reactions of d0 group 4 amides with dioxygen. Preparation of unusual oxo aminoxy complexes and theoretical studies of their formation.
Wang R, Zhang XH, Chen SJ, Yu X, Wang CS, Beach DB, Wu YD, Xue ZL., J. Am. Chem. Soc. 127(14), 2005
PMID: 15810856

Mitzel, J. Chem. Soc. Dalton Trans. (), 1996

Wieghardt, Z. Anorg. Allg. Chem. 490(), 1982

AUTHOR UNKNOWN, 0

Jana, Chem. Commun. (), 2006

Ullrich, Eur. J. Inorg. Chem. (), 2004

AUTHOR UNKNOWN, 0
Structural diversity in bishydroxylamine complexes of gallium.
Bosing P, Willner A, Pape T, Hepp A, Mitzel NW., Dalton Trans (19), 2008
PMID: 18443697
Different modes of aggregation in organoaluminium and -gallium hydroxylamides.
Mitzel NW, Lustig C, Woski M., Dalton Trans (3), 2004
PMID: 15252545

Lustig, Angew. Chem. 113(), 2001

AUTHOR UNKNOWN, 0

Mitzel, J. Am. Chem. Soc. 119(), 1997

Mitzel, Angew. Chem. 109(), 1997

AUTHOR UNKNOWN, Angew. Chem. Int. Ed. Engl. 36(), 1997

Mitzel, J. Am. Chem. Soc. 120(), 1998

Losehand, Inorg. Chem. 37(), 1998

Mitzel, J. Am. Chem. Soc. 122(), 2000
Three-membered ring or open chain molecule - (F3C)F2SiONMe2 a model for the alpha-effect in silicon chemistry.
Mitzel NW, Vojinovic K, Frohlich R, Foerster T, Robertson HE, Borisenko KB, Rankin DW., J. Am. Chem. Soc. 127(39), 2005
PMID: 16190736

AUTHOR UNKNOWN, 0

Mitzel, J. Chem. Soc. Dalton Trans. (), 2002
Synthesis, decomposition, and structural studies in the gas phase and solid state of N,N-dimethylaminoxygermane.
Mitzel NW, Losehand U, Hinchley SL, Rankin DW., Inorg Chem 40(4), 2001
PMID: 11225108

Mitzel, Organometallics 18(), 1999

AUTHOR UNKNOWN, 0
First mixed hydrazide/hydroxylamide metal aggregates.
Jana S, Berger RJ, Frohlich R, Mitzel NW., Chem. Commun. (Camb.) (38), 2006
PMID: 17003876

Ullrich, Eur. J. Inorg. Chem. (), 2006

Jana, Z. Naturforsch. B 62(), 2007
Homoleptic 12-coordinate lanthanoids with eta(2)-nitroso ligands.
Chesman AS, Turner DR, Izgorodina EI, Batten SR, Deacon GB., Dalton Trans (14), 2007
PMID: 17387395
Potassium hydroxylamine complexes.
Venugopal A, Berger RJ, Willner A, Pape T, Mitzel NW., Inorg Chem 47(11), 2008
PMID: 18461926
Hydroxylaminato yttrate and samarate complexes.
Venugopal A, Willner A, Hepp A, Mitzel NW., Dalton Trans (29), 2007
PMID: 17637986
Rare-earth metal hydroxylamide complexes.
Venugopal A, Hepp A, Pape T, Mix A, Mitzel NW., Dalton Trans (46), 2008
PMID: 19030626
Bis(hydroxylaminato)-mono(pentamethylcyclopentadienyl) rare-earth metal complexes.
Venugopal A, Pape T, Willner A, Mitzel NW., Dalton Trans (29), 2009
PMID: 20449085

Bauer, J. Org. Chem. 27(), 1962

Leaver, Dalton Trans. (), 2003
Transition metal coordination chemistry ofN,N-bis(2-{pyrid-2-ylethyl})hydroxylamine.
Belock CW, Cetin A, Barone NV, Ziegler CJ., Inorg Chem 47(16), 2008
PMID: 18646844

Sayigh, J. Org. Chem. 29(), 1964

Birmingham, J. Am. Chem. Soc. 78(), 1956

Deacon, Aust. J. Chem. 40(), 1987

Kumar, J. Mol. Struct. 875(), 2008

Semenova, Aust. J. Chem. 52(), 1999

Mitzel, J. Chem. Soc. Perkin Trans. 1 2(), 1996

Shannon, Acta Crystallogr. Sect. A 32(), 1976

Bradley, 2001

Gibbs, J. Magn. Reson. 93(), 1991

Sheldrick, Acta Crystallogr. Sect A 46(), 1990

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0
Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®
Quellen

PMID: 19774565
PubMed | Europe PMC

Suchen in

Google Scholar