Mechanistic Studies of C-C bond cleavage of nitrites by dinuclear metal cryptates
Document Type
Article
Publication Date
11-16-2009
Department
Department of Chemistry
Abstract
We previously reported that dinuclear copper(II) cryptate [Cu 2L]4+ cleaves the C-C bond of acetonitrile at room temperature to produce a cyanobridged dinuclear cryptate and methanol, whereby the reaction mechanism has not yet become clear. We have now systemically investigated this reaction, and four cryptates, [Cu2L] (ClO 4)4 (1), [Zn2L](ClO4)4 (2), [Cu2L(H2O)2](CF3SO 3)4 (5), and [Cu2L(OH)(OH2)]- (ClO4)3 (6) are reported here. Cryptates 1 and 2 can cleave the C-C bonds of acetonitrile, propionitrile, and benzonitrile at room temperature under open atmospheric conditions to give cyano-bridged cryptates [Cu2L(CN)]-(ClO4)3 (3) and [Zn 2L(CN)](ClO4]3 (4), respectively, and the corresponding alcohol. In contrast, 5 and 6 do not show any C-C bond activation of nitriles, as the interior axial positions of CuII in 5 and 6 are occupied by water/OH-. The C-C bond cleavage of (S)-(+)-2- methylbutyronitrile by 2 produced (R)-(-)2-butanol only; that is, the cleavage reaction proceeds through an SN2 pathway (Walden inversion).
Publication Title
Chemistry - A European Journal
Recommended Citation
Yang, L.,
Li, Y.,
Zhuang, X.,
Jiang, L.,
Chen, J.,
Luck, R.,
&
Lu, T.
(2009).
Mechanistic Studies of C-C bond cleavage of nitrites by dinuclear metal cryptates.
Chemistry - A European Journal,
15(45), 12399-12407.
http://doi.org/10.1002/chem.200901610
Retrieved from: https://digitalcommons.mtu.edu/michigantech-p/3567