Mixed ruthenium-iridium carbonyl cluster complexes. Synthesis of the anions [Ru3Ir2(CO)(14)](2-) and [Ru3Ir2(CO)(14)H](-) and crystal structures of their [tetraphenylphosphonium](+) salts

The reaction of Ru-3(CO)(12) and [Ir(CO)(4)](-) (as [PPh4](+) or [N(PPh3)(2 )](+) salts) yields the anion [RU3Ir2(CO)(14)](2-) (1) which has been found to derive From the intermediate [Ru3Ir(CO)(13)](-) anion. Treatment of(l) with acids gives the conjugated hydride species [Ru,Ir,(CO),,H]- (2). The t wo anions R ere characterized by single-crystal X-ray diffraction of their [PPh4](+) salts. [PPh4](2)[Ru3Ir2(CO)(14)]: space group C2/c, Z= 4, a = 22. 121(5) Angstrom, b = 10.546(5) Angstrom, ( = 25.931(5) Angstrom, beta = 103 .870(5)degrees, R = 0.052 and R-w = 0.130 for 3128 independent reflections with I > 2 sigma (I). [PPh4][Ru3Ir2(CO)(14)H]: space group P2(1)/c, Z = 8, a = 22.833(5) Angstrom b = 13.893(5) Angstrom, c = 25.810(5) Angstrom, beta = 92.650(5)degrees, R = 0.070 and R-w = 0.150 for 12141 independent reflec tions with I > 2 sigma (I). Both anions 1 and 2 have a trigonal bipyramidal metal frame. There are two independent anions in the asymmetric unit of 2 differing in their ligand stereochemistry.