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.

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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
Ausgabe
22
Seite(n)
6239-6247
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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.

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Rare-Earth-metal methylidene complexes.
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PMID: 24395606
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57 References

Daten bereitgestellt von Europe PubMed Central.


AUTHOR UNKNOWN, 0

Matignon, Ann. Chim. Phys. 8(), 1906

Jantsch, Z. Anorg. Allg. Chem. 193(), 1930

AUTHOR UNKNOWN, 0

Kagan, Tetrahedron 59(), 2003

Kagan, J. Alloys Compd. 408-412(), 2006

AUTHOR UNKNOWN, 0

Evans, Coord. Chem. Rev. 206(), 2000

Meyer, Chem. Rev. 88(), 1988

Bochkarev, Angew. Chem. 109(), 1997

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

Evans, J. Am. Chem. Soc. 122(), 2000

Bochkarev, Angew. Chem. 113(), 2001

AUTHOR UNKNOWN, Angew. Chem. Int. Ed. 40(), 2001

AUTHOR UNKNOWN, 0

Jaroschik, Organometallics 26(), 2007

Jaroschik, Angew. Chem. 121(), 2009
Dinitrogen reduction and C-H activation by the divalent organoneodymium complex [(C5H2tBu3)2Nd(mu-I)K([18]crown-6)].
Jaroschik F, Momin A, Nief F, Le Goff XF, Deacon GB, Junk PC., Angew. Chem. Int. Ed. Engl. 48(6), 2009
PMID: 19107883

AUTHOR UNKNOWN, Angew. Chem. 121(), 2009

Hitchcock, Angew. Chem. 120(), 2008
Lanthanum does form stable molecular compounds in the +2 oxidation state.
Hitchcock PB, Lappert MF, Maron L, Protchenko AV., Angew. Chem. Int. Ed. Engl. 47(8), 2008
PMID: 18189261

AUTHOR UNKNOWN, 0

Morss, Chem. Rev. 76(), 1976

Evans, Coord. Chem. Rev. 206(), 2000

Bond, Organometallics 5(), 1986

Meyer, Z. Anorg. Allg. Chem. 633(), 2007

Evans, J. Am. Chem. Soc. 110(), 1988

AUTHOR UNKNOWN, 0

Evans, J. Am. Chem. Soc. 113(), 1991

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

Ruspic, Angew. Chem. 120(), 2008
Remarkable stability of metallocenes with superbulky ligands: spontaneous reduction of Sm(III) to Sm(II).
Ruspic C, Moss JR, Schurmann M, Harder S., Angew. Chem. Int. Ed. Engl. 47(11), 2008
PMID: 18257006

Korobkov, Organometallics 28(), 2009

AUTHOR UNKNOWN, 0

Bojer, Angew. Chem. 122(), 2010
Lewis base induced reductions in organolanthanide chemistry.
Bojer D, Venugopal A, Neumann B, Stammler HG, Mitzel NW., Angew. Chem. Int. Ed. Engl. 49(14), 2010
PMID: 20191648

Meyer, Angew. Chem. 122(), 2010
Heteroleptic samarium(II) complexes by base-induced reduction.
Meyer G., Angew. Chem. Int. Ed. Engl. 49(18), 2010
PMID: 20209553
Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state.
Venugopal A, Kamps I, Bojer D, Berger RJ, Mix A, Willner A, Neumann B, Stammler HG, Mitzel NW., Dalton Trans (29), 2009
PMID: 20449090
Cationic rare-earth-metal methyl complexes: a new preparative access exemplified for Y and Pr.
Nieland A, Mix A, Neumann B, Stammler HG, Mitzel NW., Dalton Trans 39(29), 2010
PMID: 20442946

Martinez-Aguilera, Tetrahedron: Asymmetry 6(), 1995
Homoleptic rare-earth metal(III) tetramethylaluminates: structural chemistry, reactivity, and performance in isoprene polymerization.
Zimmermann M, Froystein NA, Fischbach A, Sirsch P, Dietrich HM, Tornroos KW, Herdtweck E, Anwander R., Chemistry 13(31), 2007
PMID: 17654457

AUTHOR UNKNOWN, 0

Zimmermann, Angew. Chem. 119(), 2007

Litlabø, Angew. Chem. 120(), 2008
A rare-earth metal variant of the Tebbe reagent.
Litlabo R, Zimmermann M, Saliu K, Takats J, Tornroos KW, Anwander R., Angew. Chem. Int. Ed. Engl. 47(49), 2008
PMID: 18972476
Ln(III) methyl and methylidene complexes stabilized by a bulky hydrotris(pyrazolyl)borate ligand.
Zimmermann M, Takats J, Kiel G, Tornroos KW, Anwander R., Chem. Commun. (Camb.) (5), 2007
PMID: 18209806
Amido-stabilized rare-earth metal mixed methyl methylidene complexes.
Zimmermann M, Rauschmaier D, Eichele K, Tornroos KW, Anwander R., Chem. Commun. (Camb.) 46(29), 2010
PMID: 20574561

Evans, J. Am. Chem. Soc. 116(), 1994

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

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