AU-IR AND HG-IR MIXED-METAL CARBONYL CLUSTERS - SYNTHESIS, CHARACTERIZATION, AND SOLID-STATE STRUCTURE OF [IR-6(CO)(15)(AUPPH(3))(2)] AND [IR-6(CO)(14)(HGCL)(2)](2-)
A. Ceriotti et al., AU-IR AND HG-IR MIXED-METAL CARBONYL CLUSTERS - SYNTHESIS, CHARACTERIZATION, AND SOLID-STATE STRUCTURE OF [IR-6(CO)(15)(AUPPH(3))(2)] AND [IR-6(CO)(14)(HGCL)(2)](2-), Organometallics, 14(1), 1995, pp. 186-193
The neutral cluster [Ir-6(CO)(15)(AuPPh(3))(2)] has been obtained by r
eaction of [Ir-6(CO)(15)](2-) with [AuPPh(3)](+). It crystallizes in t
he triclinic space group P1 with cell constants a = 13.160(2) Angstrom
, b = 13.714(4) Angstrom, c 18.266(3) Angstrom, alpha = 65.47(2)degree
s, beta = 110.93(2)degrees, gamma = 112.07(1)degrees, V = 2699(2) Angs
trom(3), and Z = 2. Data were collected at room temperature to a maxim
um 2 theta = 54 degrees. The final discrepancy indices were R = 0.032
and R(w) = 0.034 for 7217 independent reflections with I > 3 sigma(I).
The structure was solved by direct methods. The iridium atoms of the
cluster define an octahedral frame capped by one gold-phosphine group.
The second AuPPh(3) unit spans one Ir-Au edge. The metal skeleton of
C-1 symmetry is coordinated by twelve terminal and three edge-bridging
carbonyl groups. The dianionic [Ir-6(CO)(14)(HgCl)(2)](2-) has been p
repared from [Ir-6(CO)(15)](2-) and Hg2Cl2, HgCl2 + Hg, or HgCl2 in th
e presence of Na2CO3. The salt [PPh(4)](2)[Ir-6(CO)(14)(HgCl)(2)] crys
tallizes in the monoclinic space group Cc with cell constants a = 10.2
57(2) Angstrom, b = 46.848(4) Angstrom, c 14.639(3) Angstrom, beta = 1
07.83(2)degrees, V = 6696(4) Angstrom(3), and Z = 4. Data were collect
ed at room temperature to a maximum 2 theta = 50 degrees. The final di
screpancy indices were R = 0.037 and R(w) = 0.036 for 3619 independent
reflections with I > 3 sigma(I). The metallic framework forms an octa
hedron of iridium atoms bearing, on four non-adjacent faces, two mu(3)
-HgCl fragments and two mu(3)-CO groups. The chemical shift of the Hg-
199 NMR was found at +1508 ppm, and suggests an anomalous oxidation st
ate.