Synthesis and structural characterization of [NEt4][Fe-3(mu(3)-O)(mu(3)-AUPPh(3))(mu-CO)(3)(CO)(6)], the new [Au-6(mu(3)-S)(2)(PPh3)(6)][Fe-3(mu(3)-S)(mu-AuPPh3)(CO)(9)](2) and [Au-6(mu-S)(2)(PPh3)(6)][Fe-5(mu(3)-S)(2)(CO)(14)] ionic solids containing assemblages of cluster-cations and cluster-anions
Vg. Albano et al., Synthesis and structural characterization of [NEt4][Fe-3(mu(3)-O)(mu(3)-AUPPh(3))(mu-CO)(3)(CO)(6)], the new [Au-6(mu(3)-S)(2)(PPh3)(6)][Fe-3(mu(3)-S)(mu-AuPPh3)(CO)(9)](2) and [Au-6(mu-S)(2)(PPh3)(6)][Fe-5(mu(3)-S)(2)(CO)(14)] ionic solids containing assemblages of cluster-cations and cluster-anions, INORG CHIM, 291(1-2), 1999, pp. 372-379
The new [Fe-3(mu(3)-O)(mu(3)-AuPPh3)(mu-CO)(3)(CO)(6)](-) and [Fe-3(mu(3)-S
)(mu-AuPPh3)(CO)(9)](-) monoanionic congeners have been obtained by reactin
g the [Fe-3(mu(3)-E)(CO)(9)](2-) (E = O, S) dianions with one equivalent of
Au(PPh3)Cl. The gold adduct of the oxygen derivative has been crystallized
as tetraethylammonium and trimethylbenzylammonium salt either from THF and
n-hexane or acetone and isopropyl alcohol, and structurally characterized
in its tetraethylammonium salt (monoclinic, C2/c (No. 15), a = 15.859(2). b
= 12.859(2), c = 40.217(8) Angstrom, beta = 96.41(1)degrees Z = 8). The [F
e-3(mu(3)-S)(mu-AuPPh3)(CO)(9)](-) gold adduct, in contrast, partially reve
rts to the parent dianion upon crystallization under the above experimental
conditions, and could be precipitated only as the [Au-6(mu(3)-S)(2)(PPh3)(
6)][Fe-3(mu(3)-S)(mu-AuPPh3)(CO)(9)](2) salt (triclinic, P (1) over bar (No
. 2), a = 18.998(8), b = 19.933(8), c = 22.94(1) Angstrom, alpha = 99.91(4)
, beta = 98.91(4), gamma = 107.42(3)degrees Z = 2), by addition of an equiv
alent of the [Au-3(mu(3)-S)(PPh3)(3)](+) sulfonium cation to the reaction m
ixture. The [Fe-5(mu(3)-S)(2)(CO)(14)](2-) dianion does not form a gold add
uct even in the presence of the sulfonium cation and only the corresponding
[Au-6(mu(3)-S)(2)(PPh3)(6)][Fe-5(mu(3)-S)(2)(CO)(14)] salt could be obtain
ed. The [Fe-3(mu(3)-O)(mu(3)-AuPPh3)(mu-CO)(3)(CO)(6)](-) and [Fe-3(mu(3)-S
)(mu-AuPPh3)(CO)(9)](-) gold adducts are not isostructural and the possible
factors leading to their structural diversities are discussed. The [Au-6(m
u(3)-S)(2)(PPh3)(6)][Fe-3(mu(3)-S)(mu-AuPPh3)(CO)(9)](2) and [Au-6(mu(3)-S)
(2)(PPh3)(6)][Fe-5(mu(3)-S)(2)(CO)(14)] salts represent further examples of
ionic solids assembled from cluster-cations and cluster-anions. (C) 1999 E
lsevier Science S.A. All rights reserved.