36352-75-7Relevant academic research and scientific papers
Reactions of [(CO)3(P-P)Mn]2 with primary alcohols, where, P-P is dppe {Ph2P(CH2)2PPh2}, dppp {Ph2P(CH2)3PPh2}, dppb {Ph2P(CH2)4PPh2}, dpppe {Ph2P(CH2)5PPh2}, dtpe {(p-tol)2P(CH2)
O'Keiffe, LaKeisha S.,Mitchell, Alisha C.,Becker, Thomas M.,Ho, Douglas M.,Mandal, Santosh K.
, p. 13 - 18 (2007/10/03)
Treatment of the manganese(tricarbonyl)diphosphine dimers [(CO)3(P-P)Mn]2 (where, P-P is dppe {Ph2P(CH2)2PPh2}, dppp {Ph2P(CH2)3PPh2}, dppb {Ph2P(CH2)4PPh2}, dpppe {Ph2P(CH2)5PPh2}, dtpe {(p-tol)2P(CH2)2P(p-tol)2}, and dcpe {(chex)2P(CH2)2P( chex)2}), with 1-propanol, 1-butanol, 1-pentanol, or 1-hexanol yielded fac-(CO)3(dppe)MnH (1), fac-(CO)3(dppp)MnH (2), fac-(CO)3(dppb)MnH (3), fac-(CO)3(dpppe)MnH (4), fac-(CO)3(dtpe)MnH (5), and fac-(CO)3(dcpe)MnH (6), respectively, and the corresponding aldehydes. Also treatment of Mn2(CO)10 with P-P in 1-propanol, 1-butanol, 1-pentanol, or 1-hexanol yielded the corresponding manganese(I) hydrides (1-6) and aldehydes. Structural characterization of 5 demonstrates a manganese-hydrogen (Mn-H(1)) bond length of 1.57(3) ? which is in close agreement with the manganese-hydrogen bond length of 1.60(2) ? observed in (CO)5MnH by neutron diffraction analysis.
Conversion of a manganese-carbon-bonded complex to a manganese-oxygen-bonded complex, some reactions of manganese carbonato complexes
Li, Guang Qing,Burns, Robert M.,Mandal, Santosh K.,Bauer, Jeanette Krause,Orchin, Milton
, p. 89 - 94 (2007/10/03)
Stirring a solution of the manganese carboxylate, (dppe)(CO)3Mn-C(O)OCH3, 1, in dichloromethane saturated with water converts it to the bridging carbonato complex, (dppe)(CO)3Mn-OC(O)O-Mn(CO)3(dppe), 2. This multi-step conversion involves the in-situ transformation of a Mn-C bonded complex to a Mn-O bonded one. When 2 is stirred with HCl, it is converted quantitatively to the covalent chloride (dppe)(CO)3Mn-Cl, 11, with evolution of carbon dioxide. Similar HCl treatment of the manganese carboxylate 1 gives three compounds: the same covalent chloride, 11; the ionic chloride, [(dppe)(CO)4Mn] + Cl-, 12, and the hydride, (dppe)(CO)3Mn-H, 5. Reasonable schemes for these conversions are suggested. Heating the ionic chloride complex to its melting point converts it to the covalent chloride complex; the same transformation is accomplished by refluxing the ionic chloride in acetonitrile.
The synthesis and reactions of Mn and Re formyl complexes, fac-(P-P)M(CO)3CHO. The X-ray structure of fac-(dppp)Mn(CO)3CH2OCH3
Mandal, Santosh K.,Krause, Jeanette A.,Orchin, Milton
, p. 113 - 118 (2007/10/02)
Treatment of the salts fac- (M=Mn, Re; P-P=dppe, dppp) with NaBH4 gives the corresponding formyl complexes, fac-(P-P)M(CO)3CHO in excellent yield.Solutions of these formyls undergo spontaneous loss of CO to give the corresponding hydride
ELECTROOXIDATION OF METAL CARBONYL ANIONS. FORMATION AND REACTIVITY OF 17-ELECTRON MANGANESE(0) RADICALS
Kuchynka, D. J.,Amatore, C.,Kochi, J. K.
, p. 133 - 154 (2007/10/02)
The series of carbonylmanganese anions Mn(CO)3P2-, with P = phosphites and phosphines, undergo reversible anodic oxidation to the 17-electron radicals Mn(CO)3P2. in tetrahydrofuran solutions.The reactivity of the carbonyl-manganese radicals of Mn(CO)3P2. is evaluated in the context of hydrogen atom transfer from tributyltin hydride.The donor properties of the carbonylmanganates are strongly modulated by the ligands - the reversible oxidation potentials E1/2 of phosphine-substituted anions being significantly more negative than those of the phosphite analogs.By contrast the reactivity of the phosphine- and phosphite-substituted radicals are not differentiated by electronic factors.However steric effects (as indicated by the cone angle of the phosphite or phosphine ligand play a strong role in determining the reactivity of these 17-electron radicals.The combination of cyclic voltammetry, chronoamperometry, coulometry, and product analysis is used to establish the mechanism of hydrogen transfer from tribultyn hydride to Mn(CO)3P2. in THF solutions.The measurement of the second-order rate constants k2 for hydrogen transfer by double potential step chronoamperometry (DPSC) is described.
