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Surprising reactivity of the unsymmetrically substituted amidinate anion [MeC(NEt)(NtBu)]−
- Source :
- Journal of Organometallic Chemistry. 791:252-257
- Publication Year :
- 2015
- Publisher :
- Elsevier BV, 2015.
-
Abstract
- Three unexpected products derived from the unsymmetrically substituted amidinate anion [MeC(NEt)(NtBu)]− are reported. Treatment of 1-tert-butyl-3-ethyl-carbodiimide, tBu-N C N–Et, with 1 equiv. of methyllithium in diethyl ether afforded colorless crystals of the unusual octanuclear lithium amidinate derivative {[LiN(Et)C(Me)N(tBu)]2⋅LiN(Et)C(CH2Li)N(tBu) Et2O}2 (1) in 57% yield instead of the expected lithium amidinate Li[MeC(NEt)(NtBu)]. In the molecule of 1, one central methyl group in a trimer of Li[MeC(NEt)(NtBu)] is deprotoned and two of these partially deprotonated trimers are linked through a central eight-membered [C–N–Li–CH2]2 ring to afford the octanuclear product 1. The same reaction carried out in 1,2-dimethoxyethane (DME) solution produced the oxygen-centered, heptanuclear lithium amidinate cluster {Li[MeC(NEt)(NtBu)]}5⋅Li2O (2) (21% yield). Treatment of anhydrous praseodymium trichloride with in situ-prepared Li[MeC(NEt)(NtBu)] in Et2O/THF afforded green (THF)Li[Pr{MeC(NEt)(NtBu)}4] (3) as the first anionic tetrakis(amidinato)lanthanide(III) complex in 55% isolated yield. The molecular and crystal structures of all three new compounds have been elucidated by X-ray diffraction.
- Subjects :
- Lanthanide
Stereochemistry
Organic Chemistry
chemistry.chemical_element
Trimer
Crystal structure
Biochemistry
Medicinal chemistry
Inorganic Chemistry
chemistry.chemical_compound
Deprotonation
chemistry
Materials Chemistry
Lithium
Methyllithium
Reactivity (chemistry)
Physical and Theoretical Chemistry
Methyl group
Subjects
Details
- ISSN :
- 0022328X
- Volume :
- 791
- Database :
- OpenAIRE
- Journal :
- Journal of Organometallic Chemistry
- Accession number :
- edsair.doi...........e01f1df4c281d1ddda57c12b29dc8ce3