55971-56-7

Upstream product

• 13939-06-5 molybdenum hexacarbonyl 
• 15152-84-8 Mo(CO)5(trimethylamine) 
• 54099-81-9 2Na⁽¹⁺⁾*Mo(CO)5^(2-)=Na₂Mo(CO)5 
• 66-40-0 tetraethyl ammonium 
• 639-58-7 triphenyltin chloride 
• 71-91-0 tetraethylammonium bromide 

Relevant academic research and scientific papers

Synthesis and properties of the pentacarbonylmetalates of the group 6 metals

Reduction of the amine complexes [M(CO)5(NMe3)] (M = Cr, Mo, W) with sodium naphthalenide in THF provides a convenient route to the pentacarbonylmetalates of the group 6 metals in an innocuous solvent. The synthetic utility of the method has been demonstrated by reaction of the dianions with Ph3SnCl to give [NEt4][M(CO)5SnPh3] (M = Cr, Mo, W) in 76, 92, and 62% yield, respectively, after counterion exchange. The sodium salts of [Mo(CO)5]2- and [W(CO)5]2- cannot be handled in the solid state but can be readily separated from the NMe3 and C10H8 byproducts of the reduction. Naphthalenide reduction has also been used to prepare [W(CO)5]2- with Li+ and K+ counterions, and crystalline salts of [W(CO)5]2- and [Mo(CO)5]2- have been prepared by adding pentamethyldiethylenetriamine to Li2[W(CO)5] and a cryptand (K-2.2.1) to Na2[M(CO)5] (M = Mo, W). Crystals of the encrypted sodium salts are indefinitely stable, and a brief account is given of an X-ray diffraction study which establishes a slightly distorted trigonal-bipyramidal structure for the tungsten anion in the solid state. The IR spectra of the [Na(K-2.2.1)]+ salts in CH3CN exhibit the two band patterns expected in the carbonyl stretching region if the anions have D3h structures without counterion contact ion pairing, but ion pairing has a marked effect on solution spectra of simple alkali-metel salts of [W(CO)5]2+. The Li+ salt exhibits isocarbonyl absorptions indicating interaction with two of the equatorial carbonyls, while Na2[W(CO)5] and K2[W(CO)5] have high-energy carbonyl stretches indicative of contact ion pairing with direct M-W interaction.

Preparation of dianionic carbonyl complexes of molybdenum and tungsten

Reduction of [M(CO)5(NMe3)] (M = Cr, Mo, W) in THF with alkali naphthalides gives high purity solutions of the corresponding [M(CO)5]2- dianions. Stable crystalline salts of the [M(CO)5]2- dianions (M = Mo, W) were prepared by complexing the sodium counterions with a cryptand. Reduction of [W(CO)4(NH3){P(i-Pr)3}] with sodium naphthalide gives [W(CO)4{P(i-Pr)3}]2-, as demonstrated by reaction with Ph3SnCl and counterion exchange to give [NEt4][W(CO)4{P(i-Pr)3}SnPh3].