Manganese tetracarbonyl complexes

The behavior of cationic penta- and tetracarbonyl complexes of manganese and rhenium toward liquid NH3 at various temperatures is summarized in Table I (112). 

A second synthesis of a manganese(I) tetracarbonyl complex, namely, [Mn(CO)4(S2CNHMe)], involves the addition of carbon disulfide to [Mn(C0)4(NH2Me) ri -C(0)NHMe ] (1129). 

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... 

The synthesis of pentacarbonyl rhenium(I) halides, Re(CO)5X, succeeded from simple and complex rhenium halides below 200 atm of CO at 200° C. The compounds are extraordinarily stable and form easily, often quantitatively, from carbon monoxide and rhenium metal in the presence of other heavy metal halides or halogen sources such as CC14. Later we prepared the corresponding carbonyl halides of manganese (67) and technetium (68) from their respective carbonyls. It was found that the corresponding binuclear tetracarbonyl halides [M(CO)4X]2 (M = Mn, Re) could be made by heating the mononuclear M(CO)5X complexes (15, 69), as well as by other methods. 

It is perhaps first appropriate to consider how the coordination chemistry of lesser unsaturated derivatives evolved. In pioneering work by Coffield and his coworkers, it was demonstrated that reaction of acetylene with manganese pentacarbon-yl or methylmanganese tetracarbonyl under autoclave conditions led to production of the complex 174 (Scheme 28).248) The cyclopentadienyl unit in 174 is of course... 

When manganese vapour and a mixture of nitric oxide, trifluorophosphine and boron trifluoride are co-condensed the compound Mn(PF3)(NO)3 is produced [280]. Co-condensation of nickel and carbon dioxide results in the formation of some nickel tetracarbonyl [280]. Burdett and Turner [298] showed that co-condensation of nickel and nitrogen at 20°K resulted in a nickel—nitrogen complex. Moskovits and Ozin [299] have recently repeated the experiment and have shown from the infrared spectrum of the matrix that the major product is NiN2, with the nickel atom bonded to the end of the nitrogen molecule. 

Alkyl- and aryl-cobalt tetracarbonyls also react readily with phosphines forming acyl derivatives RCOCo(CO)3PR 3. Phosphite ligands are found to replace carbon monoxides successively forming RCOCo(CO)2L2 [193]. The replacement of two carbon monoxide ligands by phosphites under conditions where phosphine ligands will only replace one carbon monoxide, is therefore found for both cobalt and manganese complexes. Both... 

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