Nucleophilic reactions with isocyanide complexes

B. Nucleophilic Reactions with Metal Isocyanide Complexes... 

The subjects of structure and bonding in metal isocyanide complexes have been discussed before 90, 156) and will not be treated extensively here. A brief discussion of this subject is presented in Section II of course, special emphasis is given to the more recent information which has appeared. Several areas of current study in the field of transition metal-isocyanide complexes have become particularly important and are discussed in this review in Section III. These include the additions of protonic compounds to coordinated isocyanides, probably the subject most actively being studied at this time insertion reactions into metal-carbon bonded species nucleophilic reactions with metal isocyanide complexes and the metal-catalyzed a-addition reactions. Concurrent with these new developments, there has been a general expansion of descriptive chemistry of isocyanide-metal complexes, and further study of the physical properties of selected species. These developments are summarized in Section IV. 

The reaction of isocyanide complexes with nucleophiles gives metal-carbene complexes [49], which constitute an important branch of organometallic chemistry and are effective catalyst systems for a variety of processes [50, 51]. 

There are several other methods for the synthesis of carbene complexes of osmium. The reaction of a nucleophile with isocyanide complexes can result in the formation of osmium carbene complexes. Certain electron-rich alkenes add to osmium to form carbene complexes. For example. 

The reactions of isocyanide complexes with nucleophiles parallel the reactions of metal carbonyls. Alcohols were found to add across the carbon-nitrogen bond of complexed isocyanides (Badley et al., 1969, 1971). Amines... 

The reactions of nucleophilic reagents with cationic and uncharged metal carbonyl complexes have received much attention in the past, and it is not surprising that these studies have now been extended to isocyanide metal complexes. Different products in these reactions can arise by three general routes these include ligand substitution, reactions involving attack at a ligand, and reduction of the metal complex. All have been observed in reactions with metal isocyanide complexes. 

Transition metal isocyanide complexes can undergo reactions with nucleophiles to generate carbene complexes. Pt(II) and Pd(II) complexes have been most extensively investigated, and the range of nucleophilic reagents employed in these reactions has included alcohols, amines, and thiols (56) ... 

Aldol reactions of isocyanides with aldehydes are catalyzed by cationic platinum complexes having P-C-P or N-C-N ligands in the presence of a catalytic amount of an amine base to give 2-oxazolines (Equation (126)) 48S>485a>485b Platinum-coordinated a-isocyano carbanions presumably serve as nucleophiles toward aldehydes. Low to moderate enantioselectivities were obtained by using chiral platinum complexes.485 4853... 

The most common reaction of platinum(II) isocyanides is their reaction with nucleophiles. This reaction is a useful one for the formation of platinum carbene complexes, and this will be discussed in the next section. 

A cyclopentadienylcopper-fcr/-butyl isocyanide complex catalyzes the Michael addition of dimethyl methylmalonate to acrylonitrile at room temperature to give an S6% yield of the adduct 249). As the CU2O—BNC complex can also catalyze the addition of indene to methyl acrylate, the intermediate is most likely an organocopper complex. The reactions and kinetic data support the mechanism given by Eq. (118) to (120), involving metalation and nucleophilic attack by the carbanion on the olefin within the complex. Displacement of a solvent ligand by the olefin and coordination of the latter to the copper species are essential features of the mechanism. The rate of reaction is decreased if the compound with the... 

Palladium isocyanide complexes react with amines and alcohols to give palladium Carbene Complexes (equation 15) in a reaction that is a nucleophilic attack on the isonitrile carbon. These complexes easily lose a halide if it is trans to the carbene ligand, since the carbene carbon has a high trans influence. The structures of these compounds have the carbene carbon and its two heteroatom groups in one plane, which is perpendicular to the coordination plane of the Pd. 

Isocyanides, being nucleophilic, and having a greater proton affinity than the corresponding cyanides, add readily to carbocations, though the acid sensitivity of isocyanides limits the reaction to those carbocations which can be prepared under non-acidic conditions. The complex of cyclobutadiene with AICI3 provides a useful example of this type of reaction. The isocyanide can also insert into the C—Cl bond of 143. 

Organogold carbene compounds [Au(carbene)(CN) j iR ] can be obtained from com-plexed cyanides [Au(CN)m(C6F5) ] (n = 1 or 3, m = 1 and n = m = 2) by sequential alkylation (to form isocyanide complexes) and nucleophilic attack of amine" . Gold(III) diisocyanides [Au(CNR)2(CgF5)2]+ (R = Ph or p-tolyl), which can also be obtained by isocyanide substitution of ether in [Au(C6F5)2(OEt2)2] > react with hydrazobenzene NH(Ph)NHPh and hydrazine or phenyUiydrazine according to the reactions in Scheme 32 to furnish cyclic bis(carbene) and cyclic carbene-imidoyl compounds . ... 

The ligating isocyanide is activated toward electrophilic attack and aminocarbyne-type species are formed by reactions with acids or alkylating agents. The nucleophilicity of the isocyanide ligand in those electron-rich complexes is in contrast to its usual electrophilic character " reported for this ligand when it binds a metal ion in its normal or higher oxidation states. 

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