IrCl

Binary Compounds. The fluorides of indium are IrF [23370-59-4] IrF [37501-24-9] the tetrameric pentafluoride (IiF ) [14568-19-5], and JIrFg [7789-75-7]. Chlorides of indium include IrCl, which exists in anhydrous [10025-83-9] a- and p-forms, and as a soluble hydrate [14996-61-3], and IrCl [10025-97-5], Other haUdes include IrBr [10049-24-8], which is insoluble, and the soluble tetrahydrate IrBr -4H20 IrBr [7789-64-2]-, and Irl [7790-41-2], Iridium forms indium dioxide [12030-49-8], a poorly characteri2ed sesquioxide, 11203 [1312-46-5]-, and the hydroxides, Ir(OH)3 [54968-01-3] and Ir(OH) [25141-14-4], Other binary iridium compounds include the sulfides, IrS [12136-40-2], F2S3 [12136-42-4], IrS2 [12030-51 -2], and IrS3 [12030-52-3], as well as various selenides and teUurides. 

Organometallic Compounds. The predominant oxidation states of indium in organometalUcs are +1 and +3. Iridium forms mononuclear and polynuclear carbonyl complexes including [IrCl(P(C3H3)3)2(CO)2] [14871-41-1], [Ir2014(00)2] [12703-90-1], [Ir4(CO)22] [18827-81 -1], and the conducting, polymeric [IrCl(CO)3] [32594-40-4]. Isonitnle and carbene complexes are also known. 

Coordination of the dianion [S4N4] as a tridentate ligand has been established in a few cases. The complexes IrCl(CO)(S4N4)PPh3 and... 

Chloro-5-methylthiazole, 2-chlorobenzothiazole, and 2-chlorobenzox-azole oxidatively add to [IrCl(CO)(PMe2Ph)2] to yield the neutral iridium(III) carbene species 47 and 48 (X = 0, S) (73JOM(50)C54,... 

The 1961 report that Vaska s compound (IrCl(CO)(PPh3)2) reversibly binds dioxygen sparked off an intense study of addition reactions of this and related compounds that has continued unabated up to the present day [125], Vaska s compound may be prepared as yellow air-stable crystals by various reactions, such as conventional substitution... 

If X-Y bond fission occurs, the product is a 6-coordinate iridium(III) complex (Table 2.6) otherwise a 5-coordinate (or pseudo-5-coordinate) adduct is obtained in which Ir formally retains the (+1) state (Table 2.7). This distinction can be somewhat artificial IrCl(02)C0(PPh3)2 can be regarded as an iridium(III) peroxo complex. 

Adduct formation by IrCl(CO)(PPh3)2 and similar compounds results in a shift in the IR carbonyl stretching frequency (Table 2.8). 

The structures of several adducts can be rationalized on the basis [128] that in a 5-coordinate low-spin d8 tbp system, the acceptor ligands prefer to occupy an equatorial site (IrCl(CO)2(PPh3)2) whereas a 7r-donor prefers an axial site. In a square pyramidal situation, it is weakly bonded acceptors that prefer the apical position, e.g. (IrCl(S02)(C0)(PPh3)2. 

IrCl(CO)(PPh3)2 + 2PMe3 -> IrCl(CO)(PMe3)2 + 2PPh3... 

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