Hydride molybdenum

Borides are inert toward nonoxidizing acids however, a few, such as Be2B and MgB2, react with aqueous acids to form boron hydrides. Most borides dissolve in oxidizing acids such as nitric or hot sulfuric acid and they ate also readily attacked by hot alkaline salt melts or fused alkaU peroxides, forming the mote stable borates. In dry air, where a protective oxide film can be preserved, borides ate relatively resistant to oxidation. For example, the borides of vanadium, niobium, tantalum, molybdenum, and tungsten do not oxidize appreciably in air up to temperatures of 1000—1200°C. Zirconium and titanium borides ate fairly resistant up to 1400°C. Engineering and other properties of refractory metal borides have been summarized (1). 

This process has many similarities to the Phillips process and is based on the use of a supported transition metal oxide in combination with a promoter. Reaction temperatures are of the order of 230-270°C and pressures are 40-80 atm. Molybdenum oxide is a catalyst that figures in the literature and promoters include sodium and calcium as either metals or as hydrides. The reaction is carried out in a hydrocarbon solvent. 

In the chemical process industry molybdenum has found use as washers and bolts to patch glass-lined vessels used in sulphuric acid and acid environments where nascent hydrogen is produced. Molybdenum thermocouples and valves have also been used in sulphuric acid applications, and molybdenum alloys have been used as reactor linings in plant used for the production of n-butyl chloride by reactions involving hydrochloric and sulphuric acids at temperatures in excess of 170°C. Miscellaneous applications where molybdenum has been used include the liquid phase Zircex hydrochlorination process, the Van Arkel Iodide process for zirconium production and the Metal Hydrides process for the production of super-pure thorium from thorium iodide. 

In the Li-Rh system LiRh is prepared from rhodium metal foil and liq Li in a 25 at% excess of the 1 1 molar ratio. The mixture is heated in an iron crucible to 750-880°C in Ar. The direct reaction of the elements in a molybdenum crucible at 800°C for 7 d produces LiRh. Identical methods produce Lilr and Lilrj with which the rhodium compounds are isostructural . The reaction of Rh metal with LiH at 600°C gives the ternary hydrides Li4RhH4 and Li4RhH5. 

Because of the unusual nature of this molecule—it is the first molecular zinc(i) compound—it was thoroughly chemically and structurally characterized. Low-temperature X-ray structures with both molybdenum and copper radiation led to identical results (Figure 78). The structure of (r -CsMes n-Zn -CsMes) consists of two eclipsed ( 75-C5Me5)Zn units connected by a direct zinc-zinc (2.305(3) A) bond, which is substantially shorter than the sum of the covalent radii of two zinc atoms (2.50 A). The presence of bridging hydrides was discounted by the high resolution mass spectral data and by protonolysis. 

An important study using cyelopentadienyl (Cp) molybdenum species (196) has shown that reductive elimination of saturated product from an alkyl-hydride complex occurs with retention of configuration at the... 

Two significant items were confirmed in this work (a) Molybdenum, and most probably tungsten, can expand its sphere of coordination beyond 6 and (b) hydride shifts transforming olefins to allyls or 7r-allyls, via v -> (t and 77 - Tj3 processes, respectively, are feasible in metals that are known to produce active metathesis catalysts. 

Z,Z)-l,4-Dialkoxy-l,3-dienes can be readily prepared from propargyl ethers and molybdenum carbene complexes (equation 185)307. High stereoselectivity in this reaction may be due to the formation of stable vinyl hydride complex with the enol ether. 

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]. 

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

Molybdenum and tungsten carbonyl hydride complexes were shown (Eqs. (16), (17), (22), (23), (24) see Schemes 7.5 and 7.7) to function as hydride donors in the presence of acids. Tungsten dihydrides are capable of carrying out stoichiometric ionic hydrogenation of aldehydes and ketones (Eq. (28)). These stoichiometric reactions provided evidence that the proton and hydride transfer steps necessary for a catalytic cycle were viable, but closing of the cycle requires that the metal hydride bonds be regenerated from reaction with H2. 

DR. THOMAS MEYER (University of North Carolina) I feel that you have glossed over something that is actually very interesting, and that is the whole question of the Bronsted relationship. You have now observed a large number of systems, chromium, molybdenum, tungsten, which exhibit tricarbonyl anions. Have you looked at rate constants for all those species with the same hydride You would then have three bases, all with identical structures. 

POTASSIUM CYANIDE POTASSIUM HYDROXIDE LITHIUM HYDRIDE MAGNESIUM OXIDE MANGANESE MOLYBDENUM NITROGEN TRIFLUORIDE AMMONIA... 

This reaction probably proceeds via the neutral hydride that undergoes reductive elimination of germane. The stereochemistry observed (retention of configuration) is in agreement with a reductive elimination and with the assumption that the formation of the molybdenum-germanium bond proceeds with retention of configuration (cf. Sect. 3.1.2). 

Hunt s group (50, 51) have pioneered the application of the Cl source to organometallics such as the iron tricarbonyl complex of heptafulvene, whose electron impact spectrum shows (M—CO)+ as the heaviest ion, in contrast to the methane Cl spectrum with the ion as base peak. Boron hydrides (52) and borazine (53) have also been studied. The methane Cl spectrum of arenechromium and -molybdenum (54) show protonation at the metal giving a protonated parent or molecular ion. Risby et al. have studied the isobutane Cl mass spectra of lanthanide 2,2,6,6-tetramethylheptane-3,5-dionates[Ln(thd)3] (55) and 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-oetanedione [H(fod)] lanthanide complexes (56). These latter complexes have been suggested as a means of analysis for the lanthanide elements. 

Magnesium nitrate, Tin(ll) fluoride, 4693 Manganese(lV) oxide, Calcium hydride, 4705 Molybdenum(VI) oxide, Graphite, 4717 Nitric acid, Formaldehyde, 4436 Nitric acid, Formic acid, 4436 Nitric acid, Formic acid. Urea, 4436 Nitric acid, Metal thiocyanate, 4436 Oxalic acid, Urea, 0725 Ozone, Acetylene, 4846... 

Molybdenum hexacarbonyl also forms carbonylate anions, Mo(CO)5 , carbonyl halide anions, Mo(CO)5 " and carbonyl hydride anions, Mo(CO)5H in solution under controlled conditions. These species are unstable and have not been isolated. 

A sulfuric acid solution of the oxide (25-75% solution) can be reduced with tin, copper, zinc, and other reducing agents forming a blue solution of molybdenum blue which are hydrous oxides of non-stoichiometric compositions (see Molybdenum Blue). Reduction with atomic hydrogen under carefully controlled conditions yields colloidal dispersion of compounds that have probable compositions Mo204(OH)2 and Mo40io(OH)2. Reduction with lithium aluminum hydride yields a red compound of probable composition MosOtIOEOs. Molybdenum(Vl) oxide suspension in water also can be reduced to molybdenum blue by hydriodic acid, hydrazine, sulfur dioxide, and other reductants. 

A similar effect conceivably accounts for the higher Pi value (—0.74 V) (weaker net electron-donation) of the cyanide ligand estimated [15] at trans- FeH(dppe)2 with the strong donor trans-hydride, in comparison with that (—l.OV) [10] obtained at Cr(CO)5 and also proposed at trans- MoL(dppe)2) (L = CO, N2) with the strong net electron-acceptor L ligand, in spite of the lower electron-richness of the former Fe site Eg = 1.04 V) relatively to the latter (Eg = —0.11 or —0.13 V) molybdenum centers. 

The electrosynthesis of hydride complexes directly from molecular hydrogen at atmospheric pressure by reduction of Mo(II) and W(II) tertiary phosphine precursors in moderate yield has been described as also the electrosynthesis of trihydride complexes of these metals by reduction of M(IV) dihydride precursors [101,102]. Hydrogen evolution at the active site of molybdenum nitrogenases [103] is intimately linked with biological nitrogen fixation and the electrochemistry of certain well-defined mononuclear molybdenum and tungsten hydrido species has been discussed in this context [104,105]. 

Hydridotris(3,5-dimethyl-l-pyrazolyl)borate]molybdenum-(i72-acyl) complexes, such as 1, are deprotonated by butyllithium or potassium hydride to generate enolate species, such as 488.8> jjie overa]] structure of these chiral complexes is similar to that of the iron and rhenium complexes discussed earlier the hydridotris(3,5-dimethyl-l-pyrazolyl)borate ligand is iso valent to the cyclopentadienyl ligand, occupying three metal coordination sites. However, several important differences must be taken into account when a detailed examination of the stereochemical outcome of deprotonation-alkylation processes is undertaken. 

Related, achiral cc,/ -unsaturated molybdenum-( 2-acyl) complexes, such as 8, have been shown to undergo nucleophilic 1,4-conjugatc addition upon treatment with sodium borohy-dride or methyllithium to generate enolate species, such as 9 (produced by addition of hydride). Subsequent alkylation by iodomethane provides the a-alkylated product 1088. Extension of this tandem Michael addition-alkylation sequence to nonracemic molybdenum species has not yet been reported. 

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