Manganese complexes carbonyl

Herrmann and coworkers183 reported a series of Cp-manganese carbonyl complexes which bind Ge, Sn and Pb as central atoms linearly coordinated in clusters, to two Mn atoms in one series and trigonal-planar coordinated to three Mn atoms in another series 8 and 9. The group 14 atoms are double-bonded to two Mn atoms in these compounds, or carry one double bond and two single bonds to three Mn atoms. Potentiometric measurements of these compounds show irreversible reductions and oxidation by CV. No products could be isolated from either reduction or oxidation. The exceptionally high oxidation potential of (/i-Pb) r/ -CsHs )Mn(CO)2]2 as compared to the apparently similar Sn compound is noteworthy (Table 15). 

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... 

In addition to iron organometallics, manganese carbonyl complexes are also used for defluorinations upon flash-vacuum pyrolysis.149 150... 

Manganese carbenes, preparation, 5, 825 Manganese carbonyl complexes with 776-arene complexes, 5, 787 cyclopentadienyl complexes, 5, 783 with hydrocarbon ligands, complexes, 5, 776 synthesis and characteristics, 5, 761 Manganese carbonyl halides, applications and reactivity,... 

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 ... 

There have been several publications reporting cationic manganese carbonyl complexes and a number of new synthetic routes to complexes of this type have been developed. The most unusual of these is ... 

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... 

Wrighton MS, Ginley DS. Photochemistry of metal-metal bonded complexes. II. The photochemistry of rhenium and manganese carbonyl complexes containing a metal-metal bond. J Am Chem Soc 1975 97(8) 2065-2072. 

The anionic manganese carbonyl complexes [Mn(CO)4(NCS)2]" (729) and [Mn2(CO)e(CNS)4] " (278) are known, the latter containing both bridging—NCS—and terminal—NCS groups (278) [Re(CO)3(NCS)3] is also known (278, 280). However, the most interesting compounds in this category are those prepared by Wojcicki and Farona (279, 280), which are listed in Table XXIV. 

The carbyne complex 319 reacts with CO to give 320 °, which results from a double CO insertion and PMes migration, while 321 reacts with the manganese carbonyl complex 322 in refluxing toluene to give 323 °°. 

Dimeric iron or manganese carbonyl complexes such as [CpFe(C02)]2 and Mn2(CO)io, respectively, upon irradiation photocatalytically cleave carbon-halogen bonds. This leads to carbon-centered radicals which can be reduced to hydro-... 

The formation of both Mn(CO)s and the CO-loss product, Mn2(CO)9, from UV photolysis of Mn2(CO)io has been investigated by ultrafast IR spectroscopy.Density functional calculations have been performed on the ground and excited states of MnCl(CO)5, as an aid to understanding the photochemistry of MX(C0)5 complexes (M = Mn, Re X = Cl, Br, I). The lowest energy excitations are to the Mn-Cl a orbital, and these states are dissociative for both axial and equatorial CO loss, but not for Mn-Cl bond homolysis. The photochemistry of manganese carbonyl complexes (58, R = Me, benzyl R = /-Pr, p-tolyl) depends critically on the R group.CO is released with R = Me, but with R = benzyl there is efficient homolysis of the Mn-R bond. ... 

Three major classes of reaction mechanisms can be identified (1) Radical processes for cobalt and manganese carbonyl complexes that give the expected products with little stereoselectivity [11, 12, 49, 50]. Although some claims have appeared of the intervention of radicals in HDS-related hydrogenation, most of the evidence points to other types of surface mechanisms which can be better related to coordinative mechanisms therefore no further mention will be made of radical reactions in this Chapter. (2) Reactions involving Ziegler-type catalysts (a transition metal complex mixed with an alkyl aluminum co-catalyst) these poorly defined systems have proved to be difficult to study in detail [20, 22-25], and they appear rather unrelated to HDS-active... 

Another reaction of type 3 is the formation of sym-dialkylureas from primary amines and CO catalyzed by manganese carbonyl complexes ... 

The reaction of metal carbonyl dimers with silicon hydrides also probably involves an initial oxidative addition step. Chiral silyl-cobalt and silyl-manganese carbonyl complexes have been obtained through the reaction of optically active organosilicon hydrides with metal carbonyls65 68 (equation 15 and 16). Phosphine-substituted cobalt complexes were similarly obtained by reaction of a chiral hydrosilane with Co2(CO)6L2 [L = PPh3, P(OPh)3, P(c-C6Hn)3]69. 

Besides organocobalt complexes, organostibine has also been found to be able to mediate controlled/ diving polymerization of many vinyl monomers. " For example, Yamago et al reported that at 60 °C the polymerization of VAc mediated by a-dimethylstibanyl ester reached 92% conversion in 5 h and produced narrowly dispersed PVAc (PDl = 1.26), but no detailed reaction kinetics was provided in their study.Kamigaito et al. very recently found that a manganese carbonyl complex [Mn2(CO)io] coupled with an alkyl iodide ( -I)... 

Manganese carbonyl complexes containing <7-bonded ligands that are related to the celebrated tris(pyrazolyl) borate ligand see Tris(pyrazolyl)borate (4) have been... 

Various ylide complexes, e.g., (88), have been prepared by the reaction of manganese carbonyl complexes with methylenetrimethylphosphorane. The related cationic complex (89) undergoes rearrangement to the isomer (90) on treatment with base. ... 

Amides and lactones are converted to aldehydes and lactols, respectively, by a hydrosilane when a titanium alkoxide is present. Two-level reduction, i.e., of esters to ethers, is achieved by using manganese carbonyl complexes [(PhjPXCOl MnAc] as catalysts. 

Figure 7.3 Synthesis and electronic structure of bis(imino)pyridine manganese carbonyl complexes over three oxidation states.

Table 13 Mn NQR and NMR data on selected manganese carbonyl complexes Table 14 compounds chemical shifts for selected organotungsten...

Fig. 13 An HT29 colon cancer cell incubated with a manganese carbonyl complex, visualised A) by optical imaging, B) Raman imaging of integration range ca. 2800 -3050 cm , C) Raman imaging of integration range 1945 —1965 2 cm , D) is an overlay of B and C, E-G) are cross-sections of the above Raman images. ...

HaUett AJ, Baber IkA, Orpen AG, Ward BD. The coordination chemistry of tris(3,5-dimethylpyrazolyl)methane manganese carbonyl complexes synthetic, electrochemical and DPT studies. Dalton Trans. 2011 40 9276-9283. 

Manganese carbonyl complexes LMn(CO)2(THF) (L=ti -CH3C5H4 or ti -CsHs) were found to be effective in the dediazotation of diazoalkanes and in the formation of stable manganese carbene carbonyl complexes. See for examples reactions 8.23 and 8.24 [47,48]. 

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