Metal isonitriles

The mechanism of the condensation in Part D probably involves thioformylation of the metallated isocyanoacetate followed by intramolecular 1,1-addition of the tautomeric enethiol to the isonitrile. This thi2izole synthesis is analogous to the formation of oxazoles from acylation of metallated isonitriles with acid chlorides or anhydrides. " Interestingly, ethyl formate does not react with isocyanoacetate under the conditions of this procedure. Ethyl and methyl isocyanoacetate have been prepared in a similar manner by dehydration of the corresponding N-formylglycine esters with phosgene and trichloromethyl chloroformate, respectively. The phosphoryl chloride method described here was provided to the submitters by Professor U. Schollkopf and is based on the procedure of Bohme and Fuchs. The preparation of O-ethyl thioformate in Part C was developed from a report by Ohno, Koi/.uma, and Tsuchihaski. " ... 

The first transition metal isonitrilate complex reported was the tetrahedral Co-1 complex [Co(C=NPh )4] where Ph = 2,6-Me2C6H3,96 characterized by a crystal structure analysis. Oxidation yields the zerovalent dimer Co2(C=NPh )8, which features two bridging isonitrile groups. 

The imino complexes are prepared by (i) insertion into complexes containing a metal-carbon bond, (ii) oxidative addition of RX to zero-valent isonitrile complexes and subsequent insertion of the coordinated isonitrile, (iii) nucleophilic reaction of R with halogeno-metal isonitrile complexes and (iv) reaction of anionic isonitrile complexes with alkyl halides. 

This reaction is a modification of Schollkopf s oxazole synthesis2 from acid chlorides and a-metalated isonitriles (equation IT). 

A Table of corrections (q and q values) for all common stereochemistries is shown in ref. [15, Table III]. Commonly, for low valent carbonyl species, x is of the order of 0 - 0.1 V per HOMO-interacting CO, while y can be larger, as much as 0.2 - 0.3 V per HOMO-interacting isonitrile group. The isonitrile is a special case since they may be linear or bent and the electron distribution on the species does depend upon this geometry, i.e. one may suppose that the y correction allows for some variation of EL(isonitrile) value with the geometry of the metal-isonitrile bonding. 

Some metal carbonyl or metal isonitrile complexes react with isocyanates via [2+2] cycloaddition sequences to cause exchange reactions. In the first step, the carbonyl complex reacts with the isocyanate to give an isonitrile complex 63 and carbon dioxide. The generated isonitrile complex reacts subsequently with a second molecule of the isocyanate to give a carbodiimide 64 with generation of the original complex". ... 

It is assumed that compound (37) is produced by an analogous mechanism to that postulated for the synthesis of Fischer carbenes from metal-carbonyl or metal-isonitrile complexes according to Scheme 2.20. 

Many novel cluster compounds have now been prepared in this way, including mixed metal clusters. Further routes involve the oxidative fusion of dicarbon metallacarborane anions to give dimetal tetracarbon clusters such as (103) and (104) O (jjg insertion of isonitriles into inetallaborane clusters to give monocarbon meiallacarboranes such as (105) and the reaction of small ii/t/o-carboranes with alane adducts such as Et3NAlH3 to give the commo species (106) ... 

Other cyanide complexes arc discussed under the appropriate metals. In organic chemistry, both nitriles R-CK and isonitriles (isocyanidcs) R-NC are known. Isocyanides have been extensively studied as ligands (p. 926). More... 

Malatesta, L., and Bonati, F., Isonitrile Complexes of Metals. Wiley, New York (1969). 

A60. J. P. Candlin, K. A. Taylor, and D. T. Thompson, "Reactions of Transition-Metal Complexes. Elsevier, Amsterdam, 1968. A review of types of reactions of metal complexes (e.g., substitution, combination, redox) reactions with various reagents (e.g., hydrocarbons, halides, carbon monoxide, and isonitrile) and preparation of new stabilised organic systems (e.g., metallocenes, carbenes). Intended for research workers, consequently written at a fairly high level, with emphasis on organometallics. A61. H. J. Keller, NMR-Untersuchungen an Komplexverbindungen. Springer, Berlin, 1970. Expansion of review article 37.1. 

The indazoline products can also be made directly from the palladium complexes 78 by heating them with the isonitrile in toluene at 120CC.162 They are also formed in dicobalt octacarbonyl-catalyzed reactions of azo-arenes with isocyanides but in this case an alternative reaction pathway leading to indazolo[2,l- ]indazoles (79) is observed (Scheme 96).163 Products of the latter type are formed from sterically hindered isocyanides hence it is likely that in these cases a double metallation is favored over isocyanide insertion into a monometallated species (Scheme 97). 

Polymeric (isocyanide)gold(i) aryls ( gold oligo-phenylene-ethynylene-isonitriles ) were tested as electrical conductors at metal-molecule-metal junctions (7r-conjugated molecular wires), but the preparation, structure, and properties of the materials were not fully disclosed (Scheme 52).218... 

Despite a common perception that organometallic chemistry essentially belongs in the province of catalysis rather than in vivo applications because of high reactivity of metal carbon bonds, certain organometallic species have very high kinetic stability. Indeed, this point is highlighted by the present wide application of the isonitrile complex Tc(ses-tamibi), [Tc(2-methoxyisobutylisonitrile)6]+, in myocardial imaging. Rhenium tricarbonyl and cyclopentadienyl complexes offer further ex-... 

Scheme 1.37. Common patterns in the migratory insertion of zirconocene complexes with CO, isonitriles, and metal alkynylates.

Many pyridine-indole compounds are biologically active. A growing number of methods for the preparation of indolylstannanes have been developed. 2-Trialkylstannylindoles, for example, have been synthesized via directed metalation followed by reaction with tin chloride [91-93]. The latest indolylstannane syntheses include Fukuyama s free radical approach to 2-trialkylstannylindoles from novel isonitrile-alkenes [94], and its extension to an isonitrile-alkyne cascade [95]. Assisted by the chelating effect of the SEM group oxygen atom, direct metalation of 1-SEM-indole and transmetalation with BujSnCl afforded 2-(tributylstannyl)-l//-indole 108, which was then coupled with 2,6-dibromopyridine to give adduct 109. 

Multicomponent condensations have also been described in these an isonitrile, a carbonyl compound and a suitable transition metal complex are combined in one step to afford heterocycloalkylidene complexes. Examples of the use of isolated or intermediate isonitrile complexes for the preparation of aminocarbene complexes are given in Table 2.4. 

The first application of NMR diffusion measurements to determine the aggregation state of a transition metal catalyst concerned the chiral, tetranuclear Cu(i) catalysts 130-132, used in the conjugate addition reactions of anions to a,p-unsatu-rated cyclic ketones. Compounds 130-132 react wdth isonitriles to form 133-135, and do not degrade to lower molecular weight species (see Eq. (20)) [109]. 

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