LAUSR

The reaction of [HFe 4 (CO) 12 (IrCOD)] 2− ( 1 ) with CO at ambient conditions afforded [HFe 4 Ir(CO) 14 ] 2− ( 2 ), that, in turn, reacted with HBF 4 ·Et 2 O affording [Fe 4 Ir(CO) 15 ] − ( 3 ). 1 reacted with a slight excess of PPh 3 resulting in a mixture of [HFe 2 Ir 2 (CO) 10 (PPh 3 ) 2 ] − (ca. 37%) ( 5 ) and [H 2 Fe 3 Ir(CO) 10 (PPh 3 ) 2 ] − (ca. 63%) ( 6 ). 5 and 6 co-crystallized as their [NEt 4 ][H 1+x Fe 2+x Ir 2-x (CO) 10 (PPh 3 ) 2 ]·CH 2 Cl 2 (x = 0.63) salt. The reaction of 1 with Au(PPh 3 )Cl afforded [Fe 3 Ir(CO) 12 (AuPPh 3 )] 2− ( 7 ). The related hydride [HFe 3 Ir(CO) 12 ] 2− ( 9 ) was prepared from the reaction of [HFe 4 (CO) 12 ] 3− ( 8 ) with [Ir(COE) 2 Cl] 2 (COE = cyclo-octene). For sake of comparison, [HFe 3 Co(CO) 12 ] 2− ( 10 ) was obtained from 8 and Co 2 (CO) 8 . All the new clusters have been fully characterized via IR, 1 H, 13 C{ 1 H} and 31 P{ 1 H} NMR spectroscopies and their structures determined by means of single crystal X-ray crystallography. Possible isomers have been investigated by DFT calculations.