Manganese complexes carbonyl anions

Neither the palladium nor nickel catalyst described will promote the carbonylation of saturated aliphatic halides as noted above. However, this reaction can be catalyzed with cobalt (17) or iron (77) and probably with manganese (18) carbonyl anion salts. These carbonyl anions are strongly nucleophilic species and readily displace halide or other good leaving groups from primary or secondary positions giving alkyl metal carbonyl complexes. 

Analogously, reaction of group 7 metal carbonyl anions M(CO)5 (M = Mn, Re) with MeC(CFFI), gave cyclopropylcarbinyl complexes. Flowever, whereas rhenium produces the normal (/-metal bonded cyclopropylcarbinyl complex, the manganese complex furnished (cyclopropylacetyl)Mn(CO)5, where carbonyl insertion into the manganese-alkyl bond occurred (equation 56)114. 

There are no routes yet to homoleptic metal isocyanide anions. If one considers the interesting products obtained from methyl iodide additions to molybdenum (43) and manganese (44) carbonyl isonitrile anions, negatively charged isocyanide complexes should have some interesting chemistry. Also, now that a simple route to [CpFe(CNR)2]2 complexes has been devised (45), the synthesis of the anion [CpFe(CNR)2] could provide a route to a range of products including heterometal-metal bonded systems. 

Evidence for rc(-l) in complex compounds appears in the synthesis of the carbonyl anion 1Tc(CO)5], the carbonyl hydride [HTc(CO)s]°, and the heteronuclcar carbonyl anion TcFe2(CO)i2] . Their existence was suggested by a comparison of their TR absorption bands with those of the corresponding compounds of manganese and rhenium, however, no structural determinations or magnetic measurements were reported. 

Various metal-metal single o-bonded complexes have been obtained by the reaction of metal carbonyls with metal-carbon o-bonded porphyrins or by the reaction of metal carbonyl anions and chlorometalloporphyrins (Scheme 14). For example, the reaction of dimanganese carbonyl and methyl indium(III) porphyrin gives manganese pen-tacarbonyl indium porphyrin In(Por)Mn(CO)5. The same compound is isolated when chloroindium porphyrin is allowed to react with the manganese pentacarbonyl monoanion. Various iron, cobalt, tungsten, and molybdenum complexes have been prepared by these two methods. 

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... 

Density functional theory studies arene chromium tricarbonyls, 5, 255 beryllium monocyclopentadienyls, 2, 75 chromium carbonyls, 5, 228 in computational chemistry, 1, 663 Cp-amido titanium complexes, 4, 464—465 diiron carbonyl complexes, 6, 222 manganese carbonyls, 5, 763 molybdenum hexacarbonyl, 5, 392 and multiconfiguration techniques, 1, 649 neutral, cationic, anionic chromium carbonyls, 5, 203-204 nickel rj2-alkene complexes, 8, 134—135 palladium NHC complexes, 8, 234 Deoxygenative coupling, carbonyls to olefins, 11, 40 (+)-4,5-Deoxyneodolabelline, via ring-closing diene metathesis, 11, 219... 

Brunner has continued his studies on optically active manganese carbonyl complexes and has reported that treatment of Mn(CO)5Br with ort/to-Me2NC6H4PPh2 (PN) yields two enantiomers of/ac-[Mn(CO)3(PN)Br], Treatment of this complex with carbon monoxide in the presence of A1C13 produces the cation [Mn(CO)4(PN)] +, which was isolated as its hexafluorophosphated salt. Addition of menthoxide anions to the manganese carbonyl cation yields the diastereoisomers of Mn(CO)3(PN) (CO2C30H 9) however, these could not be separated due to their instability. Reaction of Mn(CO)5Br with the Schiff base NN (1) leads to formation of two isomers of... 

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