Acetonitrile iridium complex

NC2H3, Acetonitrile, iridium complex, 21 104 -----, iron complexes, 21 39-46... 

This product was characterized by its NMR spectrum and also by reaction with HC1 followed by BF3/methanol to yield methylcyanoacetate ester. The reaction occurs readily, and in the absence of detectable amounts of the oxidative addition product of acetonitrile with the iridium complex, [Hlr-(depe)2CH2CN]+. In contrast, neither Rh(depe)2Cl nor Rh(dmpe)2Cl (dmpe = Me2PCH2CH2PMe2) react with C02 in acetonitrile, though Rh(dmpe)2Cl does react with C02 in nitromethane to form the analogous nitro-acetate hydride complex, (57). 

Examples for o-phenylene scaffolds for bis-carbene ligands come from the research groups of Peris [344,345] and Herrmann [346]. Synthesis of the bis-imidazolium salt is achieved by reaction of a,a -xylene dichloride and the N-substituted imidazole. The rhodium(l) and iridinm(I) complexes can then be made by addition of the imidazolium salt to a solution of [M(cod)Cl]2 (M = Rh, Ir) in ethanol or acetonitrile (with NEtj as auxiliary base) (see Figure 3.108). The rhodium complexes were used successfully in the hydrosi-lylation of styrene [344] whereas both the rhodium and iridium complexes were used for the direct borylation of arenes making functionalised arylboronic acid esters accessible by a simple one-pot reaction [346]. 

Partial or complete displacement of the coordinated acetonitrile ligands may be achieved with monodentate ligands (e.g., phosphines ), bidentate ligands (e.g., dienes), or tridentate ligands, providing a convenient entry to a range of (i -pentamethylcyclopentadienyl)rhodium and -iridium complexes. 

Fig. 33 An iridium complex that can detect acetonitrile or propiononitrile vapor...

We also found that iridium hydrido(hydroxo) complexes like [ lrH(diphos-phine) 2( x-OH)2( x-Cl)]Cl (43) and the precursor diphosphine complexes 42 can also catalyze the hydration of nitriles. In the presence of catalyhc amounts of these complexes, heating acetonitrile and benzonitrile with excess water at 120°C gave the corresponding amides [47, 50]. 

The reversible complexing of carbon dioxide by bis[bis(l,2-diphe-nylphosphino)ethane]iridium(I) chloride, [Ir(dpe)2]Cl, in acetonitrile [Eq. (36)] (48) appears not to involve carboxylation of a cyanomethylir-idium(III) complex or its formation by decarboxylation of the cyanoacetate... 

The rates of photoinduced electron transfer (ET) reactions in a series of iridium (spacer)pyridinium complexes, [Ir(/r-dmpz)(CO)(Ph2PO-CH2-CH2-py+)]2 and [Ir( -dmpz)(CO)(Ph2PO-C6H4(CH2) -py+)]2 ( = 0 - 3), have been studied in acetonitrile solution at room temperature (99). The nuclear reorganization energies and electronic couplings in these systems have been evaluated. 

Oxidative addition of acetonitrile to a complex of iridium(I) gives a product which can be detected by NMR (dmpe dimethyldiphosphinoethane) ... 

The interaction between acetonitrile and iridium(O) complex generated elec-trochemically produces iridium(I) hydride and cyanomethyl radical [28a]. The... 

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