Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state

Venugopal A, Kamps I, Bojer D, Berger R, Mix A, Willner A, Neumann B, Stammler H-G, Mitzel NW (2009)
DALTON TRANSACTIONS (29): 5755-5765.

Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
The reaction of 1,3,5-trimethyl-1,3,5-triazacyclohexane (TMTAC) with [La{Al(CH3)(4)}(3)] resulted in C-H activation, leading to the formation of [(TMTAC) La{Al(CH3)(4)}{(mu(3)-CH2)[Al(CH3)(2)(mu(2)-CH3)](2)}] (1) containing a bis(aluminate) dianion and subsequent extrusion of methane. A similar reaction with [Y{Al(CH3)(4)}(3)] led to the formation of CH4, [TMTAC{Al(CH3)(3)}(2)] (2) and {[(TMTAC) Y][Y-2(mu(2)-CH3)][{( mu(6)-C)[Al(mu(2)-CH3)(2)(CH3)](3)}{(mu(3)-CH2)(mu(2)-CH3)Al(CH3)(2)}(2) ](3), containing a six-coordinate carbide ion and two [CH2Al(CH3)(3)](2)(-) anions. Compound 3 is a product of multiple C-H activation. This reaction was monitored by in situ H-1 NMR spectroscopy. The analogous reaction with [Sm{Al(CH3)(4)}(3)] led to the formation of 2, of [(TMTAC) Sm{(mu(2)-CH3)(CH3)(2)Al}(2){(mu(3)-CH2) Al-2(CH3)(2)}(2)](4), which contains a tris(aluminate) trianion, and [{(TMTAC) Sm}{Sm-2(mu(2)-CH3)}{( mu(6)-C)[Al(mu(2)-CH3)(2)(CH3)](3)}{(mu(3)-CH2)(mu(2)-CH3)Al(CH3)(2)}(2) ] (5), which is isostructural to 3. The products were characterised by elemental analyses (except 4, 5), 1 by multinuclear NMR spectroscopy and compounds 1, 2, 3, 4 and 5 by X-ray crystallography. Quantumchemical calculations were undertaken to support the crystallographic data analysis and confirm the structure of 3 and to compare it with an analogous compound where the central six-coordinate carbon has been replaced by oxygen. The investigations point to a mechanism of sterically induced condensation of [Al(CH3)(4)](-) groups in close proximity in the coordination spheres of the rare-earth metal atoms, which is dependent on the size of these metal atoms.
Erscheinungsjahr
Zeitschriftentitel
DALTON TRANSACTIONS
Zeitschriftennummer
29
Seite
5755-5765
ISSN
eISSN
PUB-ID

Zitieren

Venugopal A, Kamps I, Bojer D, et al. Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state. DALTON TRANSACTIONS. 2009;(29):5755-5765.
Venugopal, A., Kamps, I., Bojer, D., Berger, R., Mix, A., Willner, A., Neumann, B., et al. (2009). Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state. DALTON TRANSACTIONS(29), 5755-5765. doi:10.1039/b905271b
Venugopal, A., Kamps, I., Bojer, D., Berger, R., Mix, A., Willner, A., Neumann, B., Stammler, H. - G., and Mitzel, N. W. (2009). Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state. DALTON TRANSACTIONS, 5755-5765.
Venugopal, A., et al., 2009. Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state. DALTON TRANSACTIONS, (29), p 5755-5765.
A. Venugopal, et al., “Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state”, DALTON TRANSACTIONS, 2009, pp. 5755-5765.
Venugopal, A., Kamps, I., Bojer, D., Berger, R., Mix, A., Willner, A., Neumann, B., Stammler, H.-G., Mitzel, N.W.: Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state. DALTON TRANSACTIONS. 5755-5765 (2009).
Venugopal, Ajay, Kamps, Ina, Bojer, Daniel, Berger, Raphael, Mix, Andreas, Willner, Alexander, Neumann, Beate, Stammler, Hans-Georg, and Mitzel, Norbert W. “Neutral ligand induced methane elimination from rare-earth metal tetramethylaluminates up to the six-coordinate carbide state”. DALTON TRANSACTIONS 29 (2009): 5755-5765.

11 Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

Small molecule activation by mixed methyl/methylidene rare earth metal complexes.
Hong J, Li Z, Chen Z, Weng L, Zhou X, Zhang L., Dalton Trans 45(15), 2016
PMID: 26974519
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
Activation of isocyanates and carbon dioxide by a monomeric aluminium hydrazide as an active Lewis pair.
Hengesbach F, Jin X, Hepp A, Wibbeling B, Würthwein EU, Uhl W., Chemistry 19(41), 2013
PMID: 24038438
Syntheses, structures, and reactivities of homometallic rare-earth-metal multimethyl methylidene and oxo complexes.
Hong J, Zhang L, Yu X, Li M, Zhang Z, Zheng P, Nishiura M, Hou Z, Zhou X., Chemistry 17(7), 2011
PMID: 21294180
Substituent size effects in lewis base induced reductions in organolanthanide chemistry.
Bojer D, Neumann B, Stammler HG, Mitzel NW., Chemistry 17(22), 2011
PMID: 21503981

Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®

Quellen

PMID: 20449090
PubMed | Europe PMC

Suchen in

Google Scholar