An electrochemical study of chromium(0) complexes of arenes which have electronegative substituent groups
1981; Elsevier BV; Volume: 48; Linguagem: Inglês
10.1016/s0020-1693(00)90063-x
ISSN1873-3255
AutoresP. M. TREICHEL, G. P. ESSENMACHER, Howard F. Efner, K. J. Klabunde,
Tópico(s)Ionic liquids properties and applications
ResumoUsing cyclic voltammetry, E12 values were determined for the process Cr(arene)2 ⇄ [Cr(arene)2]+ + e (arene = C6H5R, for R = H, CF3, Cl, F, OCH3; p- and m-C6H4(CF3)2, o- and p-C6H4(CF3)Cl; 1,4(CH3)2-2-ClC6H3) in acetonitrile. Compounds with electron withdrawing groups on the arene ligands have higher E12 values indicating that they are more difficult to oxidize. This is in accord with a simple model in which withdrawal of electron density from the metal to ligands stabilizes the HOMO, a primarily metal orbital, in these systems. Possible correlations between E12 and the Hammett substituent constants, σm and σp for the substituent groups on the ligands, are investigated.
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