Benzene molybdenum

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... 

Bis(azidomethyl)oxetane, 1896 Bis(azidothiocarbonyl) disulfide, 1012a Bis(benzeneazo) oxide, 3484 Bis(jj-benzene)chromium(0), 3505 Bis(benzene)chromium dichromate, 3845 Bis(benzenediazo) sulfide, 3485 Bis(jj-benzene)iron(0), 3506 Bis(benzeneiron)—fulvalenediyl complex, 3828 Bis(jj-benzene)molybdenum(0), 3508... 

Bis(r -benzene)molybdenum(0), 3508 Bis(p3-methylidyne)rnart M/otris(pentamethylcyclopentadienylrhodium), 3907 Chloro(r 8 l,3,5,7-cyclooctatetraene)(tetrahydrofuran)lutetium, 3530... 

One of the key factors in the syntheses of benzene molybdenum complexes is the facile preparation of large quantities of bis ( 76-benzene)molybdenum. The synthesis of this compound under sealed-tube conditions has been described elsewhere.5,6 The modified procedure described here is useful for large-scale preparations. 

All operations are carried out in a dry, inert atmosphere. Schlenk apparatus capable of handling ca. 500 mL of solution is useful for the work-up of the products. Although the intermediates may be handled briefly in air, bis(f/6-benzene)molybdenum is immediately decomposed by oxygen. 

Bis(>/6-benzene)molybdenum (2 g, 7.94 mmol) in ca. 400 mL of dry benzene is treated with 1.5 mL (18.43 mmol) of allyl chloride which has been freshly distilled from P4O10. The solution is warmed to 45° in a water bath. The solution rapidly turns a red-violet color and small, purple crystals separate. After 1 hr at 40° the solution is cooled to 6° for 30 min and the light-purple supernatant liquid is decanted. The solid is washed with 100 mL of 95 % ethanol and dried in vacuo. The yield of di-/i-chloro-bis[(>/3-allyl)(t/6-benzene)molybdenum(ll)] is 1.5-1.7 g (75-85%). The solid is ground to a fine powder and transferred to a solution of 3 g (11.47 mmol) of triphenyl-phosphine in 100 mL of benzene. The mixture is stirred under reflux for 1 hr, and the red-purple solution is cooled and filtered. One hundred milliliters of 95 % ethanol is added, and the solution is concentrated to a volume of about 75 mL in vacuo. The solution is then cooled to —15° for 1 hr, and the supernatant is carefully decanted. The small, purple crystals are washed with 100 mL of 95 % ethanol and are dried in vacuo. The yield of ( 73-allyl)chloro( 76-benzene)(triphenylphosphine)molybdenum is 2.4 2.8 g (60-70% yield based on bis( /6-benzene)molybdenum). The solid is ground... 

After hydrolysis of the anion of Tc(C6Hf,)2j[AlCl4], the cation was precipitated as hexafluorophosphate. The yellow-green, diamagnetic complex salt is stable in air, acids and bases [617]. Prior to the preparation of ponderable amounts, the cation was produced by irradiating h/A(benzene)molybdenum with thermal neutrons ... 

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]. 

The green complex bis(benzene)molybdenum can be prepared similarly in up to 70% yields... 

Bis(benzene)molybdenum, in contrast to the chromium analogue, shows a very rich and varied chemistry. It has a very low molecular ionization energy in the... 

Because the Si-Cl bond is sensitive to moisture, compounds containing i-Pr2SiCl are less common. However, with careful manipulation, such confounds were characterized by NMR, MS, elemental analysis, and single-crystal X-ray diffraction analysis. " For exanple, the bis(benzene)molybdenum complex was metalated with 2 equiv f-BuLi to give the diionic intermediate 10, which was subjected to react with i-Pr2SiCl2 to give complex 11 the yield of the latter step is 37% (eq 10). ... 

The bis- r-benzene molybdenum cation is thought to disproportionate by the reaction,... 

The benzene-molybdenum bond in the postulated intermediate, 5.6a, may be thought to be analogous to the benzene-silver bond in some silver benzene complexes, see p. 29. There is infrared spectral evidence for the species arene-W(CO)5 [78d]. 

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