Comparisons in the behavior of stable copper(II), silver(II), and gold(II)complexes in the gas phase: Are there implications for condensed-phase chemistry?
Nr. Walker et al., Comparisons in the behavior of stable copper(II), silver(II), and gold(II)complexes in the gas phase: Are there implications for condensed-phase chemistry?, J AM CHEM S, 123(18), 2001, pp. 4223-4227
Experiments conducted in the gas phase have led to the formation of a serie
s of stable gold(II) complexes with nitrogen- and oxygen-containing ligands
. Such complexes are very rare in condensed-phase chemistry. However, there
is also a significant group of potential ligands, for example, H2O and NH3
, for which stable complexes could not be formed. There an strong similarit
ies between these observations and earlier results presented for silver(II)
, but both meter ions behave markedly different from copper(II). As a group
the majority of successful gold(II) ligands are characterized by being goo
d sigma donor-pi acceptor molecules; however, it is also possible to unders
tand the ability of individual ligands to stabilize the metal ion in terms
of a simple electrostatic model. Application of the latter reveals a semiqu
antitative trend between the physical properties of a ligand, e.g. ionizati
on energy, dipole moment, and polarizability, and the ligand's ability to s
tabilize either Cu(LI), Ag(II), or Au(II). The model successfully accounts
for the preference of Cu(LI) for aqueous chemistry, in comparison to the co
mplete absence of such behavior on the part of Ag(II) and Au(LT). Ligands f
rom recent examples of stable condensed-phase gold(II) complexes appear to
meet at Least one of the criteria identified from the model.