Manganese carbonylation

Mixed methyl isocyanide carbonyl manganese(I) cations [Mn(CO)5 j(Ljf]-PFj (L = CNCHj) were prepared by the standard method 154). The... 

Dimethylamino)propanalyl tetra-carbonyl manganese, AP20... 

Dipole moment measurements, first carried out in our Munich Institute by E. Weiss (108), provided evidence of the very slight polar character of the metal-CO and metal-NO bonds. Similar measurements supplied information about stereochemistry for example, of cw-I2Fe(CO)4 (108), (Ph3P)3Fe(CO)2 (51), and [Fe(CO)3SEt]2 (90), as well as of the phosphine-containing nitrosyl carbonyl manganese compounds (105). 

At first glance, all manganese products observed can readily be derived from the 19-electron carbonyl manganese radical [Mn(CO)5(L)] which is generated by electron transfer from the borate donor (Eq. 73). 

A methanol conversion rate of 14%/h at 220 °C, with ethanol accounting for 72 wt % and methane 28 wt % of the product, was obtained with iron carbonyl-manganese carbonyl catalysts. The ability to synthesize ethanol without coproduct water could lead to lower-cost processes that do not require extensive energy-consuming distillations. 

KETONES 1,3-Benzodithiolylium perchlorate. Benzyl(chloro)bis(triphenyl-phosphine)palladium. Chlorobis-(cyclopentadienyl)hydridozirconium. Iron carbonyl. Manganese(ll) iodide. Silver acetate. Thionyl chloride. Tosylmethyl isocyanide. Tri-p-carbonylhexacarbonyldiiron. 

Redox labels such as ferrocene, viologen, and (ri -cyclo"-penta"-dienyl)tri"-carbonyl manganese (cymantrenyl) may be directly conjugated to primary or secondary antibodies to serve as amperometric, voltammetric, and impedimetric reporters of immunobound conjugates. Since they invoke the faradic component of the impedance, they may be made quite sensitive. 

Scheme 25 Carbonyl manganese and rhenium complexes with tris(oxazolinyl)...

Maneb Manganeselll) acetate Manganese carbonyl Manganese cyclopentadienyl tricarbonyl Manganese 2-methylcyclopentadienyl Iricarbonyl... 

The typical SEA process uses a manganese catalyst with a potassium promoter (for solubilization) in a batch reactor. A manganese catalyst increases the relative rate of attack on carbonyl intermediates. Low conversions are followed by recovery and recycle of complex intermediate streams. Acid recovery and purification involve extraction with caustic and heat treatment to further decrease small amounts of impurities (particularly carbonyls). The fatty acids are recovered by freeing with sulfuric acid and, hence, sodium sulfate is a by-product. 

Syntheses in Solvent Systems. Very few examples of syntheses of metal carbonyls in aqueous solution are reported. An exception is the preparation of Co2(CO)g from CoSO (66% yield) or C0CI2 (56% yield) and CO at 9.6—11 MPa (95—110 atm) in aqueous ammonia at 120°C for 16—18 h (101). Triiron dodecacarbonyl is prepared almost exclusively in aqueous solution. Quantitative yields of Fe2(CO)22 have been obtained by oxidising alkaline solutions of carbonyl ferrates with manganese dioxide (102—104). 

Some metal carbonyls, such as nickel, cobalt and manganese compounds have been used to produce metallic deposition. The decomposition occurs in a stepwise manner, producing one CO(g) molecule at each step. 

---