Molybdenum alkyls

The molybdenum-alkyl mean bond dissociation enthalpies are in the expected order and in good agreement e.g. with the trend reported for Th(Cp ) R complexes (Cp = rj -C Me ) (9a). On the other hand, it is interesting to note that the group additivity rule seems to apply to the Mo-alkyl family, as shown by the excellent linear relationships 7 and 8, where N is the number of carbon atoms in the alkyl chain. 

The alkyl derivatives of thiazoles can be catalytically oxidized in the vapor phase at 250 to 400°C to afford the corresponding formyl derivatives (21). Molybdenum oxide, V2O5, and tin vanadate are used as catalysts either alone or with a support. The resulting carbonyl compounds can be selectively oxidized to the acids. 

Fig. 4. Representative structures for compounds of molybdenum(IV) (a) bis(diaIkyldithiocarbamato)oxomolybdenum(IV), MoO(S2CNR2)2, where R = alkyl (b) / Jtetracyanodioxomolybdenum(IV), Mo02(CN) (c) M03SJ3 (d) Mo3S4(SCH2CH2 )1 (e) Mo304(H20)g" (f) the Mo M S thiocubane core stmcture (g) bis(cyclopentadienyl)dichloromolybdenum(IV), CP2M0CI2, where Cp = cyclopentadienyl.

Fig. 5. Representative structures for compounds of molybdenum(III) (a) hexacholoromolybdenum(III) ion, MoClg (b) bexabis(dimethylamiHo)dimo1ybdeniim (TTT), Mo (N(CH ) ) (c) the Mo S thiocubane core stmcture (d) dichlorocyclopentadienyl triaIkylphosphinedichloromolybdenum(III), CpMo(PR2)Cl2, where Cp = cyclopentadienyl and R = alkyl.

Divalent molybdenum compounds occur in mononuclear, dinuclear, and hexanuclear forms. Selected examples are shown in Figure 6. The mononuclear compounds are mostiy in the realm of organometaUic chemistry (30—32). Seven-coordinate complexes are common and include MoX2(CO)2(PR3)2, where X = Cl, Br, and I, and R = alkyl MoCl2(P(CH3)3)4, heptakis(isonitrile) complexes of the form Mo(CNR) 2 (Fig. 6d), and their chloro-substituted derivatives, eg, Mo(CNR)3CR. The latter undergo reductive coupling to form C—C bonds in the molybdenum coordination sphere (33). 

The addition of an oxygen atom to an olefin to generate an epoxide is often catalyzed by soluble molybdenum complexes. The use of alkyl hydroperoxides such as tert-huty hydroperoxide leads to the efficient production of propylene oxide (qv) from propylene in the so-called Oxirane (Halcon or ARCO) process (79). 

Catalytic alkylation of aniline with diethyl ether, in the presence of mixed metal oxide catalysts, preferably titanium dioxide in combination with molybdenum oxide and/or ferric oxide, gives 63% V/-alkylation and 12% ring alkylation (14). 

The catalysts are primarily DCPD-soluble derivatives of tungsten and molybdenum and the activators are aluminum alkyls (63—64). Polymerization is accompHshed by mixing equal amounts of Hquid DCPD (at >32° C), one part of which contains the catalyst and the other of which contains the activator. The mixture is rapidly injected into a mold, where the polymerization takes place. Polymerization times are from under 30 seconds to several minutes, depending on the size of the part, mold temperature, and modifiers added to the polymerizate. 

As electrophilic substitutes for peracids, the use of borate ester induced decomposition of alkyl hydroperoxides and molybdenum VI peroxy-complexes have been reported in the recent literature. Although these reagents have led to the epoxidation of olefins in greater than 90% yield there are no reports yet of their application to steroid olefins. 

Homogeneous Systems Using Molybdenum and Tungsten Catalysts and Alkyl Hydroperoxides or Hydrogen Peroxide as the Terminal Oxidant... 

Compared to the tungsten-catalyzed reaction, however, the regiochemistry of the molybdenum-catalyzed alkylation is highly dependent on the structure of the nucleophile89. 

Stable enolates such as diethyl malonate anions react with allyl sulfones (or acetates) in the presence of nickel complexes to give a mixture of the a- and /-product83. The regioselectivity is generally poor in the nickel-catalyzed reaction, but the molybdenum-catalyzed reaction is selective for alkylation at the more substituted allylic site, thereby creating a quaternary carbon center84. 

The alkylation of allylic sulfides with stable anions takes place by using stoichiometric amounts of molybdenum hexacarbonyl86. Contrary to the catalytic reaction, the C —C bond formation occurs at the less hindered site of allyl groups in the stoichiometric reaction. 

Molybdenum, tris(phenylenedithio)-structure, 1,63 Molybdenum alkoxides physical properties, 2,346 synthesis, 2,339 Molybdenum blue liquid-liquid extraction, 1,548 Molybdenum cofactor, 6,657 Molybdenum complexes acrylonitrile, 2,263 alkoxides, 3,1307 alkoxy carbonyl reactions, 2,355 alkyl, 3,1307 alkyl alkoxy reactions, 2,358 alkyl peroxides oxidation catalyses, 6,342 allyl, 3,1306... 

Colona and coworkers oxidized a variety of alkyl aryl and heterocyclic sulfides to the sulfoxides using t-butyl hydroperoxide and a catalytic amount of a complex (97) derived from a transition metal and the imines of L-amino acids. Of the metals (M = TiO, Mo02, VO, Cu, Co, Fe), titanium gave the highest e.e. (21%), but molybdenum was the most efficient catalyst. The sulfoxides were accompanied by considerable sulfone125. 

Simple 1,3-dienes also undergo a thermal monocyclopropanation reaction with methoxy(alkyl)- and methoxy(aryl)carbene complexes of molybdenum and chromium [27]. The most complete study was carried out by Harvey and Lund and they showed that this process occurs with high levels of both regio-and diastereoselectivity. The chemical yield is significantly higher with molybdenum complexes [27a] (Scheme 7). Tri- and tetrasubstituted 1,3-dienes and 3-methylenecyclohexene (diene locked in an s-trans conformation) fail to react [28]. The monocyclopropanation of electronically neutral 1,3-dienes with non-heteroatom-stabilised carbene complexes has also been described [29]. 

All classes of primary amine (including primary, secondary, and tertiary alkyl as well as aryl) are oxidized to nitro compounds in high yields with dimethyl dioxirane." Other reagents that oxidize various types of primary amines to nitro compounds are dry ozone, various peroxyacids," MeRe03/H202,"" Oxone ," ° tcrt-butyl hydroperoxide in the presence of certain molybdenum and vanadium compounds, and sodium perborate." ... 

A single example of a rr-alkyl molybdenum complex was serendipitously prepared from a solution of the very light-sensitive dicarbonyl complex Mo(TPP)(CO)2. 

Within group (i), square-planar EtPt(CO)(AsPh3)Cl inserts more rapidly than six-coordinate EtIr(CO)2(AsPh3)Cl2. In THE at 40°C, the relative k s are 9 and 1. Comparison of group (ii) alkyl carbonyls reveals the order MeMn(CO)5 > CpMo(CO)3Me > CpFe(CO)2Me. The ratios of the k s are 23 I and 100 1, respectively, in THF at 25° and 50.7°C. The higher reactivity of manganese than of molybdenum is a consequence of the relative entropies, whereas the lowest reactivity of iron is caused by its Jff (Table III). 

Chiral pyridine-based ligands were, among various Ar,AT-coordinating ligands, more efficient associated to palladium for asymmetric nucleophilic allylic substitution. Asymmetric molybdenum-catalyzed alkylations, especially of non-symmetric allylic derivatives as substrates, have been very efficiently performed with bis(pyridylamide) ligands. 

Trost and Hachiya [140] studied asymmetric molybdenum-catalyzed alkylations. Interestingly, they noticed that the regioselectivity of this transformation performed with a non-symmetric allylic substrate varied according to the nature of the metal Pd-catalyzed substitutions on aryl-substituted allyl systems led to attack at the less substituted carbon, whereas molybdenum catalysis afforded the more substituted product. They prepared the bis(pyridylamide) ligand 105 (Scheme 55) and synthesized the corresponding Mo-complex from (C2H5 - CN)3Mo(CO)3. With such a catalyst, the allylic... 

Moberg et al. [146] modified further the bis(pyridylamide) ligand described by Trost for the preparation of a polymer-supported pyridylamide (113 in Scheme 60) for the microwave-accelerated molybdenum-catalyzed al-lylic alkylation. TentaGel resin was tested in the presence of high concentrations of reactants and gave, after a 30 min reaction, total conversion in the... 

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