Darstellung von Ga2[Mn(CO)5]4 und In[Mn(CO)5]3

Haupt, H.‐J.; Neumann, F.

doi:10.1002/zaac.19723940109

Cited by 17 publications

(4 citation statements)

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“…Thermal [1] or photochemical [4] activation weakens the M3M bond in compounds [Cp(CO) n M] 2 and promotes its dissociation with the formation of two 17-electron radicals [5]; this reaction is successfully used in the synthesis of polynuclear derivatives. According to [6], the rate of the reaction of [Cp(CO) 3 Cr] 2 with thallium in THF at 25oC is 250 times higher than the rate of thallium oxidation with [Cp(CO) 3 Mo] 2 under similar conditions.…”

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Oxidation of Magnesium, Indium, and Thallium with Molybdenum and Cobalt Binuclear Carbonyl Complexes in Polar Solvents

et al. 2005

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Oxidation of magnesium and thallium with bis (D 5 -cyclopentadienyltricarbonylmolybdenum) in dimethyl sulfoxide and of indium with octacarbonyldicobalt in tetrahydrofuran was studied. The formalkinetics relationships of the processes were revealed, and the intermediate and final products were identified. The apparent equilibrium constants, enthalpies and entropies of adsorption of reactants on the metal surface, and rate constants and activation energies of the reactions were determined. The reaction scheme was suggested.Redox insertion into the M3M bond in binuclear complexes (M is a main-group or transition metal) was studied in [133]. Thermal [1] or photochemical [4] activation weakens the M3M bond in compounds [Cp(CO) n M] 2 and promotes its dissociation with the formation of two 17-electron radicals [5]; this reaction is successfully used in the synthesis of polynuclear derivatives. According to [6], the rate of the reaction of [Cp(CO) 3 Cr] 2 with thallium in THF at 25oC is 250 times higher than the rate of thallium oxidation with [Cp(CO) 3 Mo] 2 under similar conditions. This relationship is consistent with the enthalpies of dissociation of the M3M bond in bis(h 5 -cyclopentadienyltricarbonylmetals) [7]: Compound [Cp(CO) 3 W] 2 [Cp(CO) 3 Mo] 2 [Cp(CO) 3 Cr] 2 I II III ,H M!M , 233.7 139.5 66.0 kJ mol !1Furthermore, in accordance with [5], the capability of metal-centered radicals generated by dissociation of binuclear complexes to abstract a halogen atom from halohydrocarbons decreases in the order h 5 -Cp(CO) 3 W > h 5 -Cp(CO) 3 Mo > h 5 -Cp(CO) 3 Cr > Co(CO) 4 . The bond energy in the corresponding dimer should vary in the opposite direction.Thus, certain success has been gained in studying the reactions under consideration and in choosing appropriate conditions to obtain the highest product yield. At the same time, some aspects of these reactions are still poorly understood. The kinetic relationships of the processes and the thermodynamic parameters of adsorption of the reactants on the metal surface are unknown. Moreover, there are no substantiated concepts concerning the reaction mechanism. It is also important to find how the reaction rate depends on the donor properties of the solvent used.The experimental results of this study show that the dependence of the rate of metal insertion into the M3M bond of a binuclear complex on the donor power of the solvent passes through a maximum, as in the case of metal oxidation with other oxidants [8]. The oxidation of magnesium and thallium is the fastest in DMSO. For the oxidation of indium, we used a solution of octacarbonyldicobalt IV in THF, since specifically in THF the dependence of the relative reaction rate on the solvent donor number DN(SbCl 5 )[9] has a maximum.The reaction of Mg with II in DMSO (C 0 0.125 M) was performed at a reactant ratio of 10 : 1 and 60oC; the mixture was stirred with a magnetic stirrer. After the reaction completion, the liquid phase was separated from the unchanged metal, and the major fraction of the solvent was removed un...

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Oxidation of Magnesium, Indium, and Thallium with Molybdenum and Cobalt Binuclear Carbonyl Complexes in Polar Solvents

et al. 2005

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“…Die Atome C(3) und C(6) nehmen die jeweils apikale Position ein. Beide Pyramiden besitzen als gemeinsame Kante die gedachte Verbindungslinie zwischen den Bruckenatomen C(4) und C (5). Der mittlere C -Mn -C(apika1)-Winkel betragt ca.…”

Section: [{(P-h)mns(co)12) (P4-in) (4) and [(Cand5)4as]z[{(p-h)mn3(co)unclassified

“…Aus der Rontgenstrukturanalyse geht hervor, daI3 die Manganatome Mn(1) und Mn (3) ohne Berucksichtigung der Hydrido-Liganden elektronisch ungesattigt sind . Demnach sollten die p-Hydrido-Liganden entlang der Kanten Mn(1) -Mn (4) oder Mn(1) -Mn (5) In (1 -Mn ( 2 ) 270,6 ( 4 ) In (1) -Mn (5) 271,4 ( 4 ) Mn ( 1 ) -Mn ( 4 ) 294,2 ( 5) Mn 294,1 (5) In ( …”

Section: Mokekiilstruktur Von [As(ch)4][{(p-h)-mn3(co)i)(plunclassified

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Darstellung von dreikernigen Carbonylmanganaten sowie deren Reaktionsprodukten mit InCl₃; Röntgenstrukturanalysen von K₃[Mn₃(μ‐CO)₂(CO)₁₀], [(C₆H₅)₄As]₂[(μ‐H)Mn₃(μ‐CO)₁₀], [{(C₆H₅)₃P}₂N]₂[μ‐H)Mn₃(CO)₁₂], [(C₆H₅)₄As]₂[{μ‐H)Mn₃(CO)₁₂}₂(μ<

et al. 1991

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Synthesis of Trinuclear Carbonylmanganates and Their Reaction Products with InCl3; X‐ray Structure Determinations of K3[Mn3(μ‐CO)2(CO)10], [(C6H5)4As]2[(μ‐H)Mn3(μ‐CO)10], [{(C6H5)3P}2N]2[μ‐H)Mn3(CO)12], [(C6H5)4As]2[{μ‐H)Mn3(CO)12}2(μ4‐In)] und [(C6H5)4As]2[{(μ‐H)Mn3(CO)12}(μ3‐In){Mn(CO)5}Cl] Mn2(CO)10 reacts with KOH in aqueous solution to give the potassium carbonylmanganate K3[Mn3(μ‐CO)2(CO)10] (1). The trianion 1 is isoelectronic with Fe3(CO)12 and is protonated with methanol to form the μ‐hydrido cluster [(μ‐H)Mn3;‐(CO)12]3⊖, which is precipitated with [{(C6H5)3P}2N]Cl as [{(C6H5)3P}2N]2[(μ‐H)Mn3(CO)12] (2), whereas the carbonyl‐bridged μ‐hydrido species [(μ‐H)Mn3(μ‐CO)2(CO)10]2⊖ seems to be trapped as the [(C6H5)4As]⊕ salt 3. The reaction of 3 with InCl3 yields the Mn‐In clusters [(C6H5)4As]2[{(μ‐H)Mn3(CO)12}2;‐(μ4‐In) (4) and [(C6H5)4As]2[{(μ‐H)Mn3(CO)12}(μ3‐In){Mn(CO)5}Cl] (5). X‐ray structure analyses have been carried out for the compounds 1 – 5.

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Reactions of Metal Carbonyls and Other Transition metal compounds

Taylor¹

1998

Inorganic Reactions and Methods

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Darstellung von Ga₂[Mn(CO)₅]₄ und In[Mn(CO)₅]₃

Cited by 17 publications

References 9 publications

Oxidation of Magnesium, Indium, and Thallium with Molybdenum and Cobalt Binuclear Carbonyl Complexes in Polar Solvents

Oxidation of Magnesium, Indium, and Thallium with Molybdenum and Cobalt Binuclear Carbonyl Complexes in Polar Solvents

Reactions of Metal Carbonyls and Other Transition metal compounds

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Darstellung von Ga2[Mn(CO)5]4 und In[Mn(CO)5]3

Cited by 17 publications

References 9 publications

Oxidation of Magnesium, Indium, and Thallium with Molybdenum and Cobalt Binuclear Carbonyl Complexes in Polar Solvents

Oxidation of Magnesium, Indium, and Thallium with Molybdenum and Cobalt Binuclear Carbonyl Complexes in Polar Solvents

Darstellung von dreikernigen Carbonylmanganaten sowie deren Reaktionsprodukten mit InCl3; Röntgenstrukturanalysen von K3[Mn3(μ‐CO)2(CO)10], [(C6H5)4As]2[(μ‐H)Mn3(μ‐CO)10], [{(C6H5)3P}2N]2[μ‐H)Mn3(CO)12], [(C6H5)4As]2[{μ‐H)Mn3(CO)12}2(μ<

Reactions of Metal Carbonyls and Other Transition metal compounds

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Darstellung von Ga₂[Mn(CO)₅]₄ und In[Mn(CO)₅]₃