Cyclopentadienyls molybdenum

Intercalates of bis(benzene)molybdenum, ( -cyclopentadienyl)titanium( 7 -cyclooctatetraene) and ( -methylcyclopentadienyl)tungsten( / -cycloheptatrienyl) into SnS2 and SnSe2 have also been investigated in detail [314, 320]. 

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.

Molecular examples of trivalent molybdenum are known in mononuclear, dinuclear, and tetranuclear complexes, as illustrated in Figure 5. The hexachloride ion, MoCk (Fig- 5a) is generated by the electrolysis of Mo(VI) in concentrated HCl. Hydrolysis of MoCP in acid gives the hexaaquamolybdenum(III) ion, Mo(H20) g, which is obtainable in solution of poorly coordinating acids, such as triflic acid (17). Several molybdenum(III) organometaUic compounds are known. These contain a single cyclopentadienyl ligand (Cp) attached to Mo (Fig. 5d) (27). 

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.

Fig. 7. Representive stmctures for compounds of molybdenum(0) (a) Mo(CO)g (b) tris(acetonitrile)tris(carbonyl)molybdenum(0) (c) bis(l,2-diphenylphosphinoethane) bis (dinitrogen) molybdenum(0), [R2PCH2CH2PR2]2Mo(N2)2, where R = CgH, also known as Mo(dppe)2(N2)2, where dppe = 1,2 — diphenylphosphinoethane (d) cyclopentadienyl tricarbonyl molybdenum(0) anion, CpMo(CO)3, where Cp = cyclopentadienyl (e)...

Thermal insertion reactions of dihydndobis(T) - cyclopentadienyl)molybdenum with tnfluoromethylacetylene give exclusively syn addition At —40 °C, hexafluoro-2-butyne inserts to the Mo-H bond to give anti addition [40] equation 30)... 

Most preparations of the intermediate racemic 3-allyl(dicarhonyl)cyclopentadieny molybdenum complexes7 2 start from sodium or potassium tricarbonyl(cyclopentadienyl)molybdate8 9 10 (4) for a simple preparation see ref 11, p 493. The allylation of 4 hy homoallylic halides, such as 4-hromo-l-butene, is accompanied by rearrangement and decarhonylationI2. (Z)-if-2-butenyl(dicarbonyl)cyclopentadienylmolybdenum (5), like other comparable complexes, exists as a mixture of endo/exo- conformers, which interconvert rapidly at room temperature12. 

Bis(i -benzene)molybdenum(0), 3514 Bis(cyeloetatetraene)uranium(0), 3708 Bis(cyclopentadienyl)bis(pentalluorophenyl)zirconium, 3830 Bis(cyclopentadienyldinitrosylchromium), 3275 Bis(cyclopentadienyl)hexalluoro-2-butynechromium, 3636 Bis(cyclopentadienyl)lead, 3294 Bis(cyclopentadienyl)magnesium, 3277 Bis(cyclopentadienyl)manganese, 3278 Bis(cyclopentadienyl)niobium tetrahydroborate, 3324... 

In a similar manner, Jt-allyl complexes of manganese, iron, and molybdenum carbonyls have been obtained from the corresponding metal carbonyl halides [5], In the case of the reaction of dicarbonyl(r 5-cyclopentadienyl)molybdenum bromide with allyl bromide, the c-allyl derivative is obtained in 75% yield in dichloromethane, but the Jt-allyl complex is the sole product (95%), when the reaction is conducted in a watenbenzene two-phase system. Similar solvent effects are observed in the corresponding reaction of the iron compound. As with the cobalt tetracarbonyl anion, it is... 

Cyclopentadienyl-manganese, -molybdenum and -tungsten anions react with organic halides to give species with five independent ligands - (Scheme 16) ... 

The S5 also occurs in sulfur vapor (7, 24). It is not clear whether the vapor contains cyclopentasulfur or catenapentasulfur, or both. Schmidt 87) proposes that 85 can be prepared from bis-ir-cyclopentadienyl-molybdenum tetrasulfide by reaction with monosulfurdichloride ... 

The retrosynthetic analysis of the 2-oxygenated carbazole alkaloids, 2-methoxy-3-methylcarbazole (37), O-methylmukonal (glycosinine) (38), 2-hydroxy-3-methylcar-bazole (52), and mukonal (53) based on the molybdenum-mediated approach led to the molybdenum-complexed cation (663) and 3-methoxy-4-methylaniline (655) as precursors (Scheme 5.51). The cationic molybdenum complex, dicarbonyl (ri -cyclohexadiene)(r -cyclopentadienyl)molybdenum hexafluorophosphate (663), required for the electrophilic substitution, was easily prepared quantitatively through known literature procedures (586,587). 

We reported the first total synthesis of l,T-bis(2-hydroxy-3-methylcarbazole) (213) using our molybdenum-mediated construction of the carbazole framework (560). The required monomer, 2-hydroxy-3-methylcarbazole (52), was obtained in three steps, and 22% overall yield, starting from dicarbonyl(ri -cyclohexa-l,3-diene)(ri -cyclopentadienyl)molybdenum hexafluorophosphate (663) and 3-meth-oxy-4-methylaniline (655) (560) (see Scheme 5.52). Finally, oxidative coupling of the monomer 52 using p-chloranil afforded l,T-bis(2-hydroxy-3-methylcarbazole) (213) in 38% yield (560) (Scheme 5.167). 

Electrochemical recognition, 39 80 anions, macrocyclic and acyclic polycobalti-cinium ligand systems, 39 134-140 cations, 39 81-133 ammonium cation, 39 128-133 crown ether and bis crow ether ligands containing bipyridyl transition metal recognition sites, 39 111 crown ether dithiocarbamate and dithi-olene complexes, 39 123-124 di-h-cyclopentadienyl-molybdenum(IV) and -tungsten(IV) crown ether complexes, 39 107-108... 

CYCLOPENTADIENYL)NITROSYL chromium, MOLYBDENUM, AND TUNGSTEN COMPLEXES... 

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