2-Amino molybdenum carbonyls

Scheme 2.29 depicts two of the first examples of microwave-assisted carbonylation reactions7. In these reactions, the temperature controls the rate of the CO release. Thus, during heating at 150°C in sealed vessels, carbon monoxide was smoothly emitted from the molybdenum carbonyl complex into the reaction mixture (Fig. 2.1, Profile A). As a result, aryl iodides and bromides underwent efficient amino carbonylation with non-hindered, aliphatic, primary and secondary amines in only 15 min, using Herrmann s palladacycle as pre-catalyst7 (Scheme 2.29). In contrast, at a reaction temperature of 210°C, carbon monoxide was liberated almost instantaneously (Fig. 2.1, Profile B).

Cyclic amino-carbenes, in molybdenum carbonyls, 5, 457 Cyclic bis(phosphine) dichlorides, with iron carbonyls, 6, 48 Cyclic carbenes, as gold atom ligands, 2, 289 Cyclic carbometallation, zirconium complexes, 10, 276 Cyclic carbozirconation characteristics, 10, 276 intermolecular reactions, 10, 278 intramolecular reactions, 10, 278 Cyclic dinuclear ylides, and gold , 2, 276 Cyclic 1,2-diols, intramolecular coupling to, 11, 51 Cyclic enones, diastereoselective cuprate additions, 9, 515 Cyclic esters, ring-opening polymerization, via lanthanide catalysis, 4, 145 Cyclic ethers... 

In 2007, Trost and McClory reported the rhodium-catalyzed cycloaromatization of terminal alkynes bearing an amino or a hydroxy group (61 and 63) into the corresponding indoles and benzofurans (62 and 64) (Scheme 21.27) [36]. As described in the preceding section, McDonald et al. reported a similar transformation catalyzed by molybdenum carbonyl complex as a catalyst [10] (see Schemes 21.23 and 21.25). Use of rhodium catalyst provided some advantages in terms of the catalyst turnover and the selectivity. The combination of [RhCl(cod)]2 and a fluorinated triarylphosphine promoted the cyclization efficiently. Later, a ruthenium version of this cyclization was reported, as shown in Scheme 21.22 [31]. 

Carbonyl compounds are produced in the homogeneous oxidation of amines by complexed molybdenum salts. Disubstituted cyanamides react with hydroxylamine to give, depending on the reaction conditions, hydroxy-guanidines or amino-oxyformamidines. Triethylamine is quatemized by dichloromethane to afford chloromethyltriethylammonium chloride in a state of very high purity. ... 

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