Dinuclear chromium(V) amino acid complexes from the reduction of chromium(VI) in the presence of amino acid ligands: XAFS characterization of a chromium(V) amino acid complex
Ha. Headlam et al., Dinuclear chromium(V) amino acid complexes from the reduction of chromium(VI) in the presence of amino acid ligands: XAFS characterization of a chromium(V) amino acid complex, INORG CHEM, 40(20), 2001, pp. 5097-5105
The first synthesis and characterization of Cr(V) complexes of non-sulfur-c
ontaining amino acids are reported. The reduction of Cr(VI) in methanol in
the presence of amino acids glycine, alanine, and 2-amino-2-methylpropanoic
acid (alpha -aminoisobutyric acid, Aib) yielded several Cr(V) EPR signals.
For the reaction involving glycine, the only Cr(V) EPR signals detected we
re those of the Cr(V)-intermediate methanol complexes, which were also obse
rved in the absence of amino acids. The reaction involving alanine yielded
one Cr(V) signal with a gi, value of 1.9754 (a(iso) = 4.88 x 10(-4) cm(-1)
and A(iso)(Cr-53) = 17.89 x 10(-4) cm(-1)). However, a solid product isolat
ed from the reaction solution was EPR silent and was characterized as a dio
xo-bridged dimeric species, [Cr-2(V)(mu -O)(2)(O)(2)(Ala)(2)(OCH3)(2)](2-),
by multiple-scattering XAFS analysis and electrospray mass spectrometry. T
he EPR spectrum of the reduction reaction of Cr(VI) in the presence of Aib
showed several different Cr(V) signals. Those observed at lower g(iso) valu
es (1.9765, 1.9806) were assigned to Cr(V)-methanol intermediates, while th
e relatively broad six-line signal at g(iso) = 2.0058 was assigned as being
due to a Cr(V) complex with coupling to a single deprotonated amine group
of the amino acid. This was confirmed by simplification of the superhyperfi
ne coupling lines from six to three when the deuterated ligand was substitu
ted in the reaction. The reduction of Cr(VI) with excess alanine or Aib lig
ands resulted in the formation of tris-chelate Cr(III) complexes, which wer
e analytically identical to complexes formed via Cr(III) synthesis methods.
The fac-[Cr(Aib)(3)] complex was characterized by single-crystal X-ray dif
fraction.