Isocyanides insertion into metal-carbon bonds

Insertion of isocyanide groups into metal-carbon bonds yields > -iminoacyl complexes reaction (n), which are briefly considered as belonging to both 1,1- and 1,2-insertions reactions on the basis of the binding. 

Polymerization of isocyanide by multiple insertion into metal-carbon bond... 

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. 

Cationic 1,2-silyl migration was proposed to be involved during the reactions of carbon monooxide and isocyanides with transition metal-carbon bonds (ligand distribution) (equation 18)55-65. Typically, the reaction of l-sila-3-zirconacyclobutane 29 with carbon monooxide afforded a dioxasilazirconacyclohexane derivative 30. The reaction was considered to proceed via a CO insertion into a Zr—C bond followed by a 1,2-silyl migration as shown in equation 1960. This type of reactions are well-documented in a review of Durfee and Roth well66. 

Facile isocyanide insertion reactions into metal-carbon, -nitrogen, -sulfur, -oxygen, - hydride, and - halide bonds have been found to readily occur. The insertion into metal-hydrides to give stable formimidines is particularly noteworthy since corresponding formyls (—CHO) are exceptionally difficult to synthesize and tend to be very unstable. There is a great deal of interest in carbon monoxide reductions, and the instability of the intermediate reduction products has made a study of the reduction process extremely difficult. Recently, however, the interaction of isocyanides with zirconium hydrides has allowed the isolation of the individual reduction steps of the isocyanide which has provided a model study for carbon monoxide reduction (39). 

Since the vanadium center of vanadocenes is electron-deficient, various vanadium derivatives are formed by the attack with PR3, CO, or unsaturated tt-donating hgands/ This reaction provides a useful synthetic method for the synthesis of jj -alkene complexes as described later. Thus formed Cp 2V(CO) (22) is converted to the cyano derivative (23, see Cyanide Complexes of the Transition Metals) on treatment with the isocyanide (Scheme 12). ( -C5Me5)2V is incubated with O2 at -78 °C to yield [(/u.-)] -C5Me503)V(0)]2 via oxygen insertion into the carbon-vanadium bond." ... 

While insertion of carbon monoxide into metal-hydrogen bonds is an elusive reaction, the analogous insertion with isocyanides and Pt-H compounds occurs readily. For example, [tmns-Pt(CNR)(H)L2]Cl undergoes a retroionization reaction and is converted to the corresponding formamidoyl complexes ... 

Insertions of Isocyanides into Metal-Carbon [Pg.643]

Polymerization of isocyanides is a thermodynamically feasible process, in agreement with the stoichiometric multiple insertion observed in reactions between metal-alkyl complexes and isocyanides. The entropy loss in the case of isocyanides is lower than for insertion of CO. Isocyanide insertions into palladium-alkyl a bonds are faster than those for the platinum(II) analogues. The latter, on the other hand, usually lead to more stable and better defined products. Insertion of isocyanides into platinum-carbon bonds has been studied extensively Reaction (j) is typical the ionic product was strongly suggested by observation that the compounds isolated under mild conditions are 1 1 electrolytes. 

The 1,2-insertion of isocyanides into a metal-carbon bond occurs readily to yield t -iminoacyl complexes... 

Just like the isoelectronic carbon monoxide, an isocyanide is an excellent ligand to metal ions. The chemistry of metal isocyanide complexes has been reviewed by Singleton and Oosthuizen. Only a few examples will be given here. Insertion of an isocyanide into a metal-carbon bond frequently occurs. It is not always clear whether the key step is electrophilic or nucleophilic attack on the coordinated isocyanide or whether the reaction is concerted. Insertion into metal-carbene and metal-carbyne complexes have been reviewed by Aumann. Coordination to the metal considerably affects the chemistry of the isocyanide. If the metal is electron-donating, as in nitrogenase-like centres, the coordinated isocyanide is apt to electrophilic attack at nitrogen cf. Section III. 

In contrast to the case of CO insertion that usually allows insertion of only one CO unit into a metal-carbon bond, isocyanides undergo multiple insertions sometimes leading to polyisocyanides [53,54]. Since the inserted isocyanide units may be regarded as imines derived from carbonyl groups, the insertion products can be regarded as polycarbonyl compounds where CO units are multiply inserted into the metal carbon bonds. The multiple insertion products of isocyanides have found applications both in organic synthesis and polymer synthesis [55]. 

Another application of pure organocopper compounds is as starting materials for the synthesis of other organocopper compounds. Treatment of [CuCisHjCFj-3] with (CF3)sCBr, for example, affords CuC(CF3)3 throu a halogen/metal exchange reaction [73] (Eqn. 2 in Scheme 1.12). A further demonstration of the applicability of pure organocopper compounds is the insertion reaction of an isocyanide into a copper-carbon bond [74], (Eqn. 3 in Scheme 1.12). 

The uranium-carbon multiple bond has an extensive insertion chemistry with polar unsaturated molecules including carbon monoxide, nitriles, isocyanides,and isocyanates. Metal carbonyls also insert into this bond to form metallaphosphoniumenolates, which undergo novel reactions... 

As stated earlier, (11.3.1), the multiple insertion of carbon monoxide into the same metal-hydrocarbyl bond is a rather elusive reaction. On the other hand, multiple insertion of isocyanide has been reported for nickel(II). For example, when the nickelfO) derivative Ni(t-BuNC)4 was treated with Mel in hexane at RT, consecutive insertion of three RNC groups was observed to give the product of reaction (e), as a consequence of a primary oxidative addition of the alkyl iodide to the nickel(O) complex. It is interesting that one of the two terminal fragments of the five-membered metallacycle is reminiscent of an arrangement of the first insertion product. 

Transition-metal-catalyzed hetero-[2 + 2 + 2]-cy-cloaddition of alkynes with carbon—heteroatom multiple bonds, such as isocyanides, carbon dioxide, nitriles, aldehydes, and ketones, provides heteroare-nes and unsaturated heterocycles. This reaction can be categorized into two groups one is the reaction of l,a>-diynes 397 with carbon—heteroatom multiple bonds, and the other is reaction of the alkynes 399, having a carbon—heteroatom multiple bond with alkynes as illustrated in Scheme 127. The reaction of 1,6 -diynes 397 proceeds through formation of the metalacyclopentadiene intermediate 398 followed by insertion of a carbon—heteroatom multiple bond, such as heterocumulenes (route a),189 nitriles (route b),190 and carbonyls (route c).191 On the other hand, the... 

Various unsaturated compounds can be inserted into the metal alkyl, aryl, and alkenyl complexes to give new organometallic complexes having various functional groups. The insertions of carbon monoxide (CO) and isocyanide (CNR) into transition metal-carbon a-bond are particularly important processes, since a carbon unit can be increased in the process and the acyl type complexes formed by the insertion processes can be subjected to further transformations to synthesize useful organic compounds. For example, the CO inserhon constitutes a fundamental step in industrially important processes such as hydroformylation of olefins, acetic acid synthesis from methanol and CO, Fischer-Tropsch process, amidocarbonylation, olefin and CO copolymerizahon processes as well as in a variety of laboratory syntheses of carbonyl containing compounds. 

Isocyanide insertion reactions into heteroatom—hydrogen, carbon-halogen, carbon—hydrogen bonds, and metal carbenes 13CSR5257. Last advances in synthesis of added value compounds and materials by laccase-mediated biocatalysis 12COC2508. 

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