Hydration and Methanolysis of Nitrile

Among these catalysts, systems obtained by the reaction between trans-[PtH(Cl)(PR3)2] (R = Me and Et) and 1 equiv. of NaOH are the most active [72]. Eor 

Some Pt complexes bearing electron-donating phosphines can also catalyze the hydration of the C=C double bond of acrylonitrile or crotonitrile and yielded P-hy-droxypropionitrile or P-hydroxybutyronitrile respectively besides the corresponding amide (Eq. 6.38) [22, 75], Among the platinum phosphine complexes examined, [Pt(PEt3)3] (26a), carrying less bulky ligands, was the most effective for the hydration of the olefmic bond. The present catalyst system was ineffective for hydration of other olefins, however. 

Several cationic palladium(II) aqua complexes, [Pd(H20)4], cis-[PdL(H20)2] (L = en, methionine methyl ester, l,5-dithiacycloocta-3-ol), and [Pd(dien)(H20)], serve as the active catalyst for the selective hydration of various nitriles to the corresponding carboxamides, e.g., CHCI2CN was hydrated to CHCl2C(0)NH2 in the presence of 

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]. 

Very recently Chin et al. reported Ir complex-catalyzed hydration as well as the first example of methanolysis of nitriles [75]. Hydration of RCN (R = Me, MeCH=CH, Ph) is catalyzed by [Cp Ir(Tl -CH2CHCHPh)(NCR)]OTf (R = Me, 

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Kostic et al. recently reported the use of various palladium(II) aqua complexes as catalysts for the hydration of nitriles.456 crossrefil. 34 Reactivity of coordination These complexes, some of which are shown in Figure 36, also catalyze hydrolytic cleavage of peptides, decomposition of urea to carbon dioxide and ammonia, and alcoholysis of urea to ammonia and various carbamate esters.420-424, 427,429,456,457 Qggj-jy palladium(II) aqua complexes are versatile catalysts for hydrolytic reactions. Their catalytic properties arise from the presence of labile water or other solvent ligands which can be displaced by a substrate. In many cases the coordinated substrate becomes activated toward nucleophilic additions of water/hydroxide or alcohols. New palladium(II) complexes cis-[Pd(dtod)Cl2] and c - Pd(dtod)(sol)2]2+ contain the bidentate ligand 3,6-dithiaoctane-l,8-diol (dtod) and unidentate ligands, chloride anions, or the solvent (sol) molecules. The latter complex is an efficient catalyst for the hydration and methanolysis of nitriles, reactions shown in Equation (3) 435... 

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