15444-76-5Relevant articles and documents
TRANSITION METAL NITROSYLS AS NITROSYLATION AGENTS. VI. LIGAND REARRANGEMENT BETWEEN THE CARBONYLMANGANESE COMPLEXES + AND 10-n(PR3)n>, AND BIS(HALOGENODINITROSYLCOBALT)
Oltmanns, Peter,Rehder, Dieter
, p. 263 - 272 (1985)
The UV-induced nitrosylation of neutral and cationic carbonylmanganese compounds by 2 (X = Cl, Br, I) is a complex reaction involving the transfer of ligands usually considered as two- (CO and PR3, PR3 = PEtPh3, P(i-Bu)3, P(O-i-Pr)3), one- (X), and three-electron donors (NO).The cationic complexes are converted into MnBr2, while and its mono- and disubstituted phosphine derivatives readily yield (L = CO, THF, PR3), cis- (X = Cl, Br, I) and (L = CO, PR3).Reactivity and product spectrum vary considerably with the starting materials.The only reaction of preparative interest is the conversion of to by 2. 55Mn and 59Co NMR characteristics are reported.An optimized preparative route to and its 55Mn NMR spectroscopic feature is also described.
Formation of metal-metal bonds by ion-pair annihilation. Dimanganese carbonyls from manganate(-I) anions and manganese(I) cations
Lee,Kuchynka,Kochi
, p. 1886 - 1897 (2008/10/08)
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.
STERIC EFFECTS OF PHOSPHINE LIGANDS ON THE PHOTOCHEMISTRY PF Mn2(CO)10
Busetto, C.,Mattucci, A. M.,Cernia, E. M.,Bertani, R.
, p. 183 - 188 (2007/10/02)
The photochemistry of Mn2(CO)10 in the presence of phosphine ligands has been investigated.Steric hindrance by the phosphine molecules influences the products of the photolysis reaction.With ethyldiphenylphosphine disubstituted symmetrical species are obt
