Substituent Size Effects in Lewis Base Induced Reductions in Organolanthanide Chemistry

Bojer D, Neumann B, Stammler H-G, Mitzel NW (2011)
Chemistry 17(22): 6239-6247.

Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
The reaction of the tripodal 1,3,5-trialkyl-1,3,5-triazacyclohexanes (L= cyclo-[N(R) CH2](3), R= Et, iPr, tBu), with [Sm(AlMe4)(3)] resulted in the formation of divalent samarium complexes of the constitution [{LnSm(AlMe4)(2)}(m)] (n, m= 1,2) under ethane extrusion. These compounds were characterised by single-crystal X-ray diffraction and elemental analyses. Simultaneous occurrence of Lewis base induced reduction and C-H-activation reactions is observed. The ratio of products depends on the bulkiness of the N-alkyl substituent R. The reaction of [Sm(AlMe4)(3)] with 1,3,5-triisopropyl-1,3,5-triazacyclohexane (TiPTAC) in benzene afforded the inversion-symmetric dimer [{(TiPTAC)(eta(3)-AlMe4) Sm}(2)(mu(2)-AlMe4)(2)], whereas in toluene the pseudo-samarocene [(TiPTAC)(2)Sm(eta(1)-AlMe4)(2)] was obtained. The trisaluminate [(TiPTAC)-Sm{(mu 2-Me)(Me2Al)}(2)(mu(3)-CH2)(2)AlMe2)] was found to be the C-H-activation product. In the case of the particular bulky 1,3,5-tri-tert-butyl-1,3,5-triazacy clohexane (TtBuTAC), the reaction led to the formation of the dimeric [{(TtBuTAC)(eta(3)-AlMe4) Sm}(2)(mu(2)-AlMe4)(2)] even in toluene in comparably high yields. The decrease of the steric demand to ethyl groups in 1,3,5-triethyl- 1,3,5-triazacyclohexane (TETAC) afforded the samarocene-like [(TETAC)(2)Sm(eta(1)-AlMe4)(2)] in lower yields. The resulting divalent samarium compounds are found to be stable with respect to reagents like dinitrogen, conjugated olefins and polycyclic aromatic systems.
Erscheinungsjahr
Zeitschriftentitel
Chemistry
Band
17
Zeitschriftennummer
22
Seite
6239-6247
ISSN
PUB-ID

Zitieren

Bojer D, Neumann B, Stammler H-G, Mitzel NW. Substituent Size Effects in Lewis Base Induced Reductions in Organolanthanide Chemistry. Chemistry. 2011;17(22):6239-6247.
Bojer, D., Neumann, B., Stammler, H. - G., & Mitzel, N. W. (2011). Substituent Size Effects in Lewis Base Induced Reductions in Organolanthanide Chemistry. Chemistry, 17(22), 6239-6247. doi:10.1002/chem.201002707
Bojer, D., Neumann, B., Stammler, H. - G., and Mitzel, N. W. (2011). Substituent Size Effects in Lewis Base Induced Reductions in Organolanthanide Chemistry. Chemistry 17, 6239-6247.
Bojer, D., et al., 2011. Substituent Size Effects in Lewis Base Induced Reductions in Organolanthanide Chemistry. Chemistry, 17(22), p 6239-6247.
D. Bojer, et al., “Substituent Size Effects in Lewis Base Induced Reductions in Organolanthanide Chemistry”, Chemistry, vol. 17, 2011, pp. 6239-6247.
Bojer, D., Neumann, B., Stammler, H.-G., Mitzel, N.W.: Substituent Size Effects in Lewis Base Induced Reductions in Organolanthanide Chemistry. Chemistry. 17, 6239-6247 (2011).
Bojer, Daniel, Neumann, Beate, Stammler, Hans-Georg, and Mitzel, Norbert W. “Substituent Size Effects in Lewis Base Induced Reductions in Organolanthanide Chemistry”. Chemistry 17.22 (2011): 6239-6247.

5 Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

Trimethylaluminum: Bonding by Charge and Current Topology.
Stammler HG, Blomeyer S, Berger RJ, Mitzel NW., Angew Chem Int Ed Engl 54(46), 2015
PMID: 26390916
Rare-earth metal methylidene complexes with Ln3(μ3-CH2)(μ3-Me)(μ2-Me)3 core structure.
Schädle D, Meermann-Zimmermann M, Maichle-Mössmer C, Schädle C, Törnroos KW, Anwander R., Dalton Trans 44(41), 2015
PMID: 26418665
Rare-Earth-metal methylidene complexes.
Kratsch J, Roesky PW., Angew Chem Int Ed Engl 53(2), 2014
PMID: 24395606
Lutetium-methanediide-alkyl complexes: synthesis and chemistry.
Li S, Wang M, Liu B, Li L, Cheng J, Wu C, Liu D, Liu J, Cui D., Chemistry 20(47), 2014
PMID: 25284379
Rare-earth-metal dialkynyl dimethyl aluminates.
Nieland A, Mix A, Neumann B, Stammler HG, Mitzel NW., Chemistry 19(25), 2013
PMID: 23616205

Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®

Quellen

PMID: 21503981
PubMed | Europe PMC

Suchen in

Google Scholar