Molybdenocene complexes

Catalytic Ionic Hydrogenation of Ketones by Molybdenocene Complexes... 

Hydride transfer reactions from [Cp2MoH2] were discussed above in studies by Ito et al. [38], where this molybdenum dihydride was used in conjunction with acids for stoichiometric ionic hydrogenations of ketones. Tyler and coworkers have extensively developed the chemistry of related molybdenocene complexes in aqueous solution [52-54]. The dimeric bis-hydroxide bridged dication dissolves in water to produce the monomeric complex shown in Eq. (32) [53]. In D20 solution at 80 °C, this bimetallic complex catalyzes the H/D exchange of the a-protons of alcohols such as benzyl alcohol and ethanol [52, 54]. 

Very related to the titanium chemistry described above are experiments with resembling molybdenocene complexes. If the molybdenum-diphenyl-acetylene complex Cp2Mo(PhC=CPh) is used as starting material, no C-C linkage reaction takes place with carbon dioxide. Instead, a crystalline solid was isolated whose x-ray proved the formation of a molybdenum-carbon dioxide complex [85] (Equation 15). 

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). 

Indenyl-fluorenyl systems, propylene polymerization, 4, 1068 Indenylidenes, in ROMP initiation, 11, 633 7]5-Indenyl ligand, in molybdenocene dihalides, 5, 573 Indenyl ligands, in cobalt(III) complexes, 7, 20 7]5-Indenyl ligands, in rhodium alkene complexes, 7, 197 2-(Indenyl)—phenoxo complexes, with mono-Cp Ti(IV),... 

Molecular recognition, in Rh Cp complexes, 7, 155 Molecular weight, in alkene living polymerizations, 11, 715 Moller-Plesset calculations, as perturbation method, 1, 646 Molten salts, and ionic liquids, 1, 848 Molybdacarboranes, synthesis, 3, 216 Molybdenocene dichloride, bioorganometallic chemistry,... 

Molybdenocene dihalides, associated chemistry, 5, 573 Molybdenocene dihydrides monomeric complexes, 5, 568 multimetallic complexes, 5, 570 protonation studies, 5, 570 Molybdenocenes... 

Multimetallic complexes, molybdenocene dihydrides, 5, 570 Multimetallic nickel-alkynes, synthesis and reactivity, 8, 145 Multinuclear chromium(II) complexes, with halides, alkyls,... 

In addition to monocyclopentadienyl dimers, various molybdenocene derivatives can form dimers, as shown in equation (33). This is one example of a vast range of organic ligands that bridge metal-metal bonded complexes. Another example is one of the several products obtained by reaction of diphenylacetylene and molybdenum carbonyl (equation 34). 

The molybdenum analog of chromocene see Metallocene Complexes) [CP2M0] (molybdenocene) is not stable and has only been isolated using matrix isolation techniques see Matrix Isolation). The IR, magnetic circular dichroism spectra of the matrix isolated [CP2M0] were interpreted in terms of a paramagnetic metallocene, with parallel rings. 

In addition to zerovalent Group 10 metals, ansa-molybdenocene dihydride reacted with nitriles upon liberation of dihydrogen by photoirradiation (Scheme 1.21) [31]. Acetonitrile underwent oxidative addition of the C-CN bond to the molybdenum center. On the other hand, when the complex was treated with bulkier pivalonitrile, the side-on coordination complex was formed. 

The first reported pesticide hydrolyses by an organometallic complex, which are the paraoxon and parathion hydrolysis by the aqueous molybdenocene dichloride (CP2M0CI2), have been reported. The synthesis and structural characterisation of a new one-to-one charge-transfer salt ferromagnet which is constructed from decamethylchromocene and dimethylcyanofumarate have been... 

The complex (OT-Ph5Cs)2Mo is of interest since the unsubstituted analogue, molybdenocene, is unknown. It is one of the products of the reactions between diphenylacetylene and molybdenum hexacarbonyl [116], and it forms red crystals which are rather unreactive. Oxidation with bromine gives a green, paramagnetic (3 5 B.M.) salt of stoicheiometry... 

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