Iridium compounds IrCl3

The gold compound AuC1(PC13) also forms stable solvolysis products from alcohols however, reduction occurs in water (2, 51). Surprisingly, it has been reported that the iridium compound IrCl3(PCl3)3 does not solvolyze in alcohols (35,70). 

In contrast to this behavior, the corresponding iridium compound [IrCl3(PCl3)3] does not solvolyze in alcohols. These reactivities reflect the effect of the metal ion on the electron density at the phosphorus atom. Some studies of the effect of coordination on the ethylenimine molecule have recently been reported by Edwards et al. (47). Although the ring in... 

Synthesis. The principal starting material for synthesis of iridium compounds is iridium trichloride hydrate [14996-61-3], IrCl3-a H2 0. Another useful material for laboratory-scale reactions is [Ir20l2(cod)2] [12112-67-3]. 

The trimesityl of iridium can be made by reaction of IrCl3(tht)3 with MesMgBr, while IrMes4 can be oxidized to the cationic iridium(V) species [IrMes4]+, also tetrahedral (with concomitant slight Ir-C bond changes from 1.99-2.04 A in the neutral compound to 2.004-2.037 A in the cation). Another iridium(V) species, IrO(Mes)3 has been made [190], it has a tetrahedral structure (lr=0 1.725 A). 

Chloro- and other halo- containing carbonyl compounds of iridium may also be synthesized under mild conditions. Unlike [Rh(CO)2Cl]2, [Ir(CO)2Cl] is not obtainable by the direct reaction of an iridium chloride solution with CO. Instead, [Ir(CO)2Cl2]n (48) is obtained in low yields by reaction between IrCl3-H20 and carbon monoxide. The predominant mononuclear compound obtained upon carbonylation of iridium chloride salts is the tricarbonyl [Ir(CO)3Cl] (49), which appears in the sohd state to be a polymeric array consisting of stacking square-planar Ir(CO)3Cl units with short fr-Ir bonds. Even though [Ir(CO)3Cl] is polymeric, it is sublimable and is stiU a convenient source of iridium(I) containing carbon monoxide. (49) will react with a number of nucleophiles to form mononuclear iridium carbonyl complexes. 

Isolation of the compound employs an aqueous workup . Both IrCl3 and trisfaetyl-acetonate)iridium are converted to Ir(/ -C3H5)3 by treatment with C3H5MgCl in THF at 50°C . 

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