Manganese carbonyl 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 Reaction of Manganese Carbonyl Halides with CNC H, and CNCH3 (Tetrahydrofuran) ... 

Recently proof has been reported for a heterometallic bimolecular formation of aldehyde from a manganese hydride and acylrhodium species [2], Phosphine free, rhodium carbonyl species show the same kinetics as the cobalt system, i.e. the hydrogenolysis of the acyl-metal bond is rate-determining. Addition of hydridomanganese pentacarbonyl led to an increase of the rate of the hydroformylation reaction. The second termination reaction that takes place according to the kinetics under the reaction conditions (10-60 bar, 25 °C) is reaction (3). The direct reaction with H2 takes place as well, but it is slower on a molar basis than the manganese hydride reaction. 

Finally, manganese carbonyl complexes also show potential for effecting interesting phase transfer catalyzed carbonylation reactions. Alkynes react with carbon monoxide and methyl iodide in methylene chloride, using 5N NaOH as the aqueous phase, benzyl-triethylammonium chloride as the phase transfer catalyst, and either bromopentacarbonylmanganese or dimanganese decacarbonyl to afford... 

Table 1 Reactions of manganese carbonyl compounds with polydeniate phosphines...

Manganese carbonyl, Mn2(CO)io, when treated with tetracyclone at 140-150°, gives an air-sensitive product which on hydrolysis gives the T-cyclopentadienyl complex (LII) 215). Manganese carbonyl does not react with dimcthylacetylene in sunlight, but duroquinone was formed in a similar reaction of the alkyne with [Mn(CO)6] 1 155). Mn(—1) is iso-electronic with Fe(0), and it is suggested that the unstable quinone com-... 

Bromopentacarbonylmanganese, Mn(CO)5Br (1). This yellow metal carbonyl halide is obtained in 73% yield by reaction of manganese carbonyl with Br2 in CC14 at 40°.1... 

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. 

The first metallocarborane of this geometry to be synthesized was an unexpected product. In an attempt to prepare a ten-vertex manganese carbonyl complex, the C2B7Hii2 ion, discussed in Section VII, was reacted with BrMn(CO)5. Surprisingly, the only metal-containing compound isolated from the reaction mixture had just 6 boron atoms (36, 50). The course of the reaction may be outlined as follows ... 

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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