Manganese carbonyl derivatives, reactions

This reaction is used with different boron halides and manganese carbonyl derivates in 12 at RT to yield B—Mn compounds (Table 1). 

The cationic manganese carbonyl derivative Mn(CO)4(phen)+ has been isolated as the Co(CO)4 and Mn(CO)5 salts (445) and the technetium derivatives Tc(CO)s(phen)X are also known. The color is a function of the halogen X, changing from colorless (X = Cl), through bright brown (X = Br), to brown (X = I) (374). The reaction of bipyridyl with pentacarbonyliron induces disproportionation (375) this can also occur when bis(l,3-cyclohexadiene)tetracarbonyldicobalt is the reactant. However, [L2(CO)4Co2] has been prepared 62). 

Reaction of the manganese and rhenium carbonyls, M2(CO)10, with Ru3(CO)12 or Os3(CO)12 in a 3 1 ratio yields the products [M(CO)5]2M (CO)4, with M = Re or Mn, M = Ru or Os. These are considered to be linear trinuclear metal systems. The only other trinuclear carbonyl derivative isolated is OsCo2(CO)n, obtained as one of a number of compounds from the reaction of Co2(CO)8 with H2Os(CO)4. No structural data are available for this compound (241). 

The first six entries in this section of Table X (entries 93-98) relate to attempted insertion reactions of fluoroalkenes or fluoroalkynes into Si-Mn or Si-Fe bonds. Even in the successful cases, yields are generally low, and in some instances (e.g., entry 94) MesSiF is lost from the insertion product to leave a fluoroalkenyl manganese carbonyl. In the case of the iron hydrido compound in entry 98, there is formal loss of hydrogen to give the binuclear derivative [CljSiFelCO). ... 

Following our early studies (89, 90), we have recently investigated derivatives of manganese carbonyl obtained from reactions between Mn(CO)5X (X usually Br) and organic sulfur ligands (93). Manganese carbonyl chelate complexes are formed in which sulfur is covalently bonded to manganese, or forms a coordinate bond as an electron donor. 

When octahedral alkylpentacarbonyl derivatives of manganese(I) undergo carbon monoxide insertion assisted by a nucleophile L different from carbon monoxide (L = tertiary phosphines, amines, CO, etc.), the cis product is initially formed this observation, however, is not sufficient to permit one to distinguish between the alkyl migration mechanism [reaction (a)] and the insertion of a precoordinated carbonyl group into the manganese-carbon bond [reaction (e)]. In both cases mutually cis positions are involved. 

Derivation Reaction of methylcyclopentadiene with manganese carbonyl. 

An analogous reaction carried out on niobium and tantalum pentachlorides is reported to give the carbonyl derivatives [Na(diglyme)2][M(CO)6] (M = Nb, Ta) (63). Similar formation of a sodium derivative of a metal carbonyl as an intermediate may also occur in the following preparations of chromium (42) and manganese (64) carbonyls with elemental sodium as the reducing agent... 

The stoichiometries of anionic metal carbonyls follow from the requirement of inert gas configuration for the metal atom. It is apparent, for example, why the usual carbonyl anions of vanadium, manganese, and cobalt have the formulas [V(CO)6] , [Mn(CO)5] , and [Co(CO)4]-, respectively. In addition, in almost all neutral metal carbonyl derivatives, such as those prepared by reactions involving alkali metal derivatives of metal carbonyls, the metal atom will also have the inert gas configuration. A very few exceptions will arise in these the metal atom will have one electron less than the inert gas... 

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