Molybdenum complexes bonding

Table 1. Metal—Metal Bonding in Molybdenum Complexes and Clusters...

Secondary amines can be added to certain nonactivated alkenes if palladium(II) complexes are used as catalysts The complexation lowers the electron density of the double bond, facilitating nucleophilic attack. Markovnikov orientation is observed and the addition is anti An intramolecular addition to an alkyne unit in the presence of a palladium compound, generated a tetrahydropyridine, and a related addition to an allene is known.Amines add to allenes in the presence of a catalytic amount of CuBr " or palladium compounds.Molybdenum complexes have also been used in the addition of aniline to alkenes. Reduction of nitro compounds in the presence of rhodium catalysts, in the presence of alkenes, CO and H2, leads to an amine unit adding to the alkene moiety. An intramolecular addition of an amine unit to an alkene to form a pyrrolidine was reported using a lanthanide reagent. 

However, when the X-ray crystal structure of the MoFe protein was examined, it was clear that homocitrate could not directly hydrogen bond to the histidine, since the carboxylate group and imidazole are stacked parallel to each other in the crystal. Nevertheless, as noted in the previous section, studies on model complexes have suggested that homocitrate can become monodentate during nitrogenase turnover, with the molybdenum carboxylate bond breaking to open up a vacant site at molybdenum suitable for binding N2. 

Olefin-metathesis is a useful tool for the formation of unsaturated C-C bonds in organic synthesis.186 The most widely used catalysts for olefin metathesis include alkoxyl imido molybdenum complex (Schrock catalyst)187 and benzylidene ruthenium complex (Grubbs catalyst).188 The former is air- and moisture-sensitive and has some other drawbacks such as intolerance to many functional groups and impurities the latter has increased tolerance to water and many reactions have been used in aqueous solution without any loss of catalytic efficiency. 

When applying these methods to the study of molybdenum complexes Voityuk and Rosch [25, 41] found that the use of the AMI core-repulsion function (Eq. 5-6) led to some systematic deviations for some Mo—X bond lengths. To address these problems, important changes to the core-repulsion function were made by the introduction of bond-specific parameters (omo-x and 8 io-x, Eq. 5-9) [22, 25], The idea of using bond-specific core repulsion parameters is not new, since the AMI parameterisation of boron used bond-specific Gaussian functions to improve the final results [42],... 

The formation of 2H-pyrroles (21) and a pyrrole derivative (22) from the reaction of 3-phenyl-2//-azirines and acetylenic esters in the presence of molybdenum hexacarbonyl is intriguing mechanistically (Schemes 24, 25).53 Carbon-nitrogen bond cleavage must occur perhaps via a molybdenum complex (cf. 23 in Scheme 26) but intermediate organometallic species have not yet been isolated.53 Despite the relatively poor yields of 2H-pyrrole products, the process is synthetically valuable since the equivalent uncatalyzed photochemical process produces isomeric 2H-pyrroles from a primary reaction of azirine C—C cleavage54 (Scheme 24). 

From the energetics point of view, the epoxidation act should occur more easily (with a lower activation energy) in the coordination sphere of the metal when the cleavage of one bond is simultaneously compensated by the formation of another bond. For example, Gould proposed the following (schematic) mechanism for olefin epoxidation on molybdenum complexes [240] ... 

The key step involves C-H bond activation, and produces a molybdenum complex with hydride and ketone ligands from the alkoxide ligand. Subsequent... 

Despite many applications of the iron-mediated carbazole synthesis, the access to 2-oxygenated tricyclic carbazole alkaloids using this method is limited due to the moderate yields for the oxidative cyclization [88,90]. In this respect, the molybdenum-mediated oxidative coupling of an arylamine and cyclohexene 2a represents a complementary method. The construction of the carbazole framework is achieved by consecutive molybdenum-mediated C-C and C-N bond formation. The cationic molybdenum complex, required for the electrophilic aromatic substitution, is easily prepared (Scheme 23). 

Olefin metathesis proceeds via reversible formation of metallacyclobutanes by [2 + 2] cycloaddition (Figure 1.7). The precise pathway for such a cycloaddition has been calculated for molybdenum complexes such as 1 (Figure 1.6) [9]. These calculations suggest that although Mo-C and C-C bond formation is concerted the Mo-C bond is formed more quickly than the C-C bond. It was also found, beautifully consistent with experimental results, that the activation barrier for [2 + 2] cycloaddition is lowered by increasingly electron-withdrawing alkoxy ligands. 

Asymmetric Synthesis Using a Chiral Molybdenum Catalyst In olefin metathesis, a double bond is cleaved and a double bond is formed. Thus, a chiral carbon center is not constructed in the reaction. To realize the asymmetric induction by ring-closing metathesis, there are two procedures a kinetic resolution and desym-metrization of symmetric prochiral triene. Various molybdenum complexes are synthesized in order to explore the viabihty of these approaches (Figure 6.2). 

The phosphine complexes provide a thermal route to other molybdenocene adducts since the molybdenum-phosphorus bond appears to be labile. When solutions of [Mo(7 5-C5H5)2PEt3] react with CO or diphenylacetylene, formation of the corresponding adduct results (see Reaction 11). 

The absence of evidence for a ligating hydrogen suggests the formulation of the product as [Mo(dppe)2] or its dimer. The relatively low solubility of the complex has thus far prevented molecular weight measurements. An ortho-metallated derivative, which might be expected, would be expected to show evidence for a molybdenum-hydride bond. The overall photochemical reaction that is consistent with this formulation and with the quantity of hydrogen released is given in Reaction 12. 

Simple oxidation/reduction has also been studied for a wide range of isocyanide complexes. Again those complexes containing mainly molybdenum-carbon bonds have been reviewed in... 

Molybdenum Complexes Containing One or More Metal-Metal Bonds... 

Complexes Involving Multiple Molybdenum-Nitrogen Bonds 1340... 

The vibrational spectra of oxomolybdenum(V) complexes display an intense band in the range 940 to 1020 cm-1 due to v(Mo—Ot) 5,8° the higher frequencies, corresponding to the shorter molybdenum-oxygen bonds, are found in square pyramidal complexes, in which there is no ligand trans to the oxo group. 

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