86708-28-3

Upstream product

• 27674-37-9 (acetonitrile)pentacarbonylmanganese(I) cation 
• 672-66-2 Dimethyl(phenyl)phosphine 
• 52745-57-0 Mn(CO)3(CH₃CN)(P(CH₃)2C₆H₅)2⁽¹⁺⁾ 
• 55029-83-9 [Mn(CO)3(acetonitrile)3]⁽¹⁺⁾ 
• 49865-17-0 fac-(OC)3Mn(NCMe)3⁽¹⁺⁾ 
• 104911-20-8 fac-{(OC)3Mn(NCMe)2(PMe₂Ph)}BF₄ 
• 52721-00-3 fac-(OC)3Mn(NCMe)2(PMe₂Ph)⁽¹⁺⁾ 
• 54039-60-0 fac-[Mn(CO₃)(MeCN)3]PF₆ 
• 52745-57-0 fac-(OC)3Mn(NCMe)(PMe₂Ph)2⁽¹⁺⁾ 
• 16940-66-2 sodium tetrahydroborate 
• 10170-69-1 dimanganese decacarbonyl 
• 104911-21-9 fac-{(OC)3Mn(NCMe)(PMe₂Ph)2}PF₆ 
• 86708-27-2 Mn(CO)3(CH₃CN)2(P(CH₃)2C₆H₅)⁽¹⁺⁾ 
• 21331-06-6 hexamanganese(I) 

Downstream Products

• 104911-21-9 Mn(CO)3(NCCH₃)(P(CH₃)2(C₆H₅))2⁽¹⁺⁾*PF₆^(1-)=[Mn(CO)3(NCCH₃)(P(CH₃)2(C₆H₅))2]PF₆ 

Relevant academic research and scientific papers

Electroreduction of carbonylmanganese(I) cations. Mechanism of ligand substitution and hydride formation via manganese(0) intermediates

Hydridomanganese(I) complexes (OC)3MnL2H are the principal products from a series of acetonitrile derivatives of carbonylmanganese cations, i.e., (OC)3Mn(NCMe)nL3-n+ (I), when the reductions are carried out electrochemically in the presence of added phosphines L. Cyclic voltammetric studies show that the conversion to the hydride can be formulated in three discrete stages. First, the carbonylmanganese cation such as (OC)3Mn(NCMe)3+ with n = 3 undergoes an electrocatalytic ligand substitution with added L to form the bis(phosphine) complex (OC)3Mn(NCMe)L2+ via labile 19-electron Mn(0) intermediates as in Scheme V. Second, the substitution product (OC)3Mn(NCMe)L2+ is reduced to the Mn(0) radical (OC)3Mn(NCMe)L2?; which is common to all cationic precursors irrespective of the degree of prior phosphine coordination in the precursor I (i.e., n = 1, 2). Third, the hydridomanganese product is derived by hydrogen atom transfer to the carbonyl ligand of the 19-electron intermediate (OC)3Mn(NCMe)L2? to form the formyl complex (OC)2Mn(NCMe)L2CHO, followed by the electrocatalytic extrusion of the coordinated ligand (MeCN) as in Scheme III. The third stage is established in the reductive conversion of the cationic (OC)4Mn(PPh3)2+ to the hydride (OC)3Mn(PPh3)2H by the observation of the intermediate (OC)3Mn(PPh3)2CHO during cyclic voltammetry. A competition to form the carbonylmanganate (OC)3MnL2- as a byproduct of reduction is also delineated.

Manganese(0) radicals and the reduction of cationic carbonyl complexes: Selectivity in the ligand dissociation from 19-electron species

Products and stoichiometry for the cathodic reduction of the series of carbonylmanganese(I) cations Mn(CO)5L+, where L - CO, MeCN, pyridine, and various phosphines, derive from 1-electron transfer to generate the 19-electron radicals Mn(CO)5L? as reactive intermediates. The CO derivative Mn(CO)6+ affords mainly the anionic Mn(CO)5- by the facile ligand dissociation of Mn(CO)6? to the 17-electron radical Mn(CO)5? followed by reduction. The acetonitrile and pyridine derivatives Mn(CO)5NCMe+ and Mn(CO)5py+ produce high yields of the dimer Mn2(CO)10 by an unusual and highly selective heterolytic coupling of Mn(CO)5- and the reactant cation. Structural factors involved in the conversion of 19-electron radicals to their 17-electron counterparts are examined in the reduction of the graded series of phosphine derivatives Mn(CO)5P+, where P = triaryl- and trialkylphosphines. The formation of the hydridomanganese complexes HMn(CO)4P is ascribed to hydrogen atom transfer to the 19-electron radicals Mn(CO)5P? followed by extrusion of CO. The lability of carbonylmanganese radicals is underscored by rapid ligand substitution to afford the bis(phosphine) byproduct HMn(CO)3P2.

Electrosynthesis of Hydridometal Carbonyls. Rapid Ligand Substitution in Transient Mn0 Intermediates from the Reduction of Carbonylmanganese(I) Cations

Unusually enhanced rates of multiple ligand substitutions are observed during the convenient synthesis of hydridomanganese complexes by the cathodic reduction of carbonylmanganese cations.