Send to

Choose Destination
Chemistry. 2009 Nov 16;15(45):12399-407. doi: 10.1002/chem.200901610.

Mechanistic studies of C-C bond cleavage of nitriles by dinuclear metal cryptates.

Author information

MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies and School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.


We previously reported that dinuclear copper(II) cryptate [Cu(2)L](4+) cleaves the C-C bond of acetonitrile at room temperature to produce a cyano-bridged dinuclear cryptate and methanol, whereby the reaction mechanism has not yet become clear. We have now systemically investigated this reaction, and four cryptates, [Cu(2)L](ClO(4))(4) (1), [Zn(2)L](ClO(4))(4) (2), [Cu(2)L(H(2)O)(2)](CF(3)SO(3))(4) (5), and [Cu(2)L(OH)(OH(2))](ClO(4))(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 [Cu(2)L(CN)](ClO(4))(3) (3) and [Zn(2)L(CN)](ClO(4))(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 Cu(II) 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 S(N)2 pathway (Walden inversion).

[Indexed for MEDLINE]

Supplemental Content

Loading ...
Support Center