71427-83-3

Upstream product

• 15529-62-1 Mn₂(CO)8(triphenyl phosphite)2 

Downstream Products

• 10170-69-1 dimanganese decacarbonyl 
• 15529-62-1 Mn₂(CO)8(triphenyl phosphite)2 
• 24476-72-0 Mn₂(CO)9(triphenyl phosphite) 
• 105228-19-1 cis-hydridomanganese tetracarbonyl triphenylphosphite 
• 15444-76-5 Mn₂(CO)8(ethyldiphenylphosphine)2 
• 19568-52-6 tetracarbonylhydrido(triphenyl phosphite)manganese 
• 109335-77-5 Mn₂(CO)8(ethyldiphenylphosphine)(triphenyl phosphite) 
• 104419-63-8 tetracarbonylhydrido(dimethylphenylphosphine)manganese 
• 55029-78-2 Mn₂(CO)8(dimethylphenylphosphine)2 
• 109335-81-1 Mn₂(CO)8(dimethylphenylphosphine)(triphenyl phosphite) 
• 63588-37-4 Mn₂(CO)8(tri-p-tolylphosphine)2 
• 104419-62-7 tetracarbonylhydrido(tri-p-tolylphosphine)manganese 
• 109335-76-4 Mn₂(CO)8(triphenyl phosphite)(tri-p-tolylphosphine) 
• 104350-79-0 tetracarbonylhydrido(diethylphenylphosphine)manganese 

Relevant academic research and scientific papers

Formation of metal-metal bonds by ion-pair annihilation. Dimanganese carbonyls from manganate(-I) anions and manganese(I) cations

The coupling of the anionic Mn(CO)5- and the cationic Mn(CO)6+ occurs upon mixing to afford the dimeric Mn2(CO)10 in essentially quantitative yields. Dimanganese decacarbonyl is formed with equal facility from the coupling of Mn(CO)5- with Mn(CO)5(py)+ and Mn(CO)5(NCMe)+. By way of contrast, the annihilation of Mn(CO)4PPh3- with Mn(CO)6+ yields a pair of homo dimers Mn2(CO)10 and Mn2(CO)8(PPh3)2 together with the cross dimer Mn2(CO)9PPh3. Extensive scrambling of the carbonylmanganese moieties also obtains with Mn(CO)4P(OPh)3- and Mn(CO)5PPh3+, as indicated by the production of Mn2(CO)8[P(OPh)3]2, Mn2(CO)8[P(OPh)3](PPh3), and Mn2(CO)8(PPh3)2 in more or less statistical amounts. These diverse Mn-Mn couplings can be accounted for by a generalized formulation (Scheme VI), in which the carbonylmanganese anions Mn(CO)4P- and the cations Mn(CO)5L+ undergo an initial electron transfer to produce Mn(CO)4P? and Mn(CO)5L?, respectively. The behaviors of these 17- and 19-electron radicals coincide with those independently generated in a previous study of the anodic oxidation of Mn(CO)4P- and the cathodic reduction of Mn(CO)5L+, respectively. The facile associative ligand substitution of 17-electron carbonylmanganese radicals by added phosphines provides compelling evidence for the interception of Mn(CO)4P? and its interconversion with 19-electron species in the course of ion-pair annihilation. The reactivity trend for the various ion pairs qualitatively parallels the driving force for electron transfer based on the oxidation and reduction potentials of Mn(CO)4P- and Mn(CO)5L+, respectively, in accord with the radical-pair mechanism in Scheme VI.

CARBONYLATION AND HYDROGENATION OF cis-CH3Mn(CO)4L, SUBSTITUTIONAL REACTIVITY OF cis-HMn(CO)4L, AND BINUCLEAR ELIMINATION BETWEEN cis-CH3Mn(CO)4P(OPh)3 AND cis-HMn(CO)4P(OPh)3 (L = CO, PPh3, P(OPh)3, PBu3 AND P(OMe)3)

Several reactions of cis-CH3Mn(CO)4L and cis-HMn(CO)4L, have been investigated.The carbonylation of cis-CH3Mn(CO)4L (L = CO, P(OPh)3, P(OMe)3, and PBu3) shows a very small ligand effect, indicating a transition state that has little unsaturation.Reaction with H2 has very similar observed rate constants and activation parameters to the carbonylation.The hydrides, cis-HMn(CO)4L (L = P(OPh)3, PPh3 and PBu3), are remarkably unreactive toward substitution, requiring temperatures of 100 deg C.A radical mechanism is most likely.Reactions of cis-HMn(CO)4P(OPh)3 with cis-CH3Mn(CO)4P(OPh)3 and cis-HMn(CO)4PBu3 with CH3C(O)Mn(CO)5 occur at temperatures where methyl migration is readily established and the hydride complexes are unreactive.Thus methyl migration, followed by coordination to a bridging hydride, is indicated for these binuclear reductive elimination reactions.