37523-64-1Relevant academic research and scientific papers
Synthesis and structural studies of phosphorus carbonyl manganacycles containing the tetraphenyldiselenoimidodiphosphinato ligand
Germán-Acacio, Juan Manuel,Reyes-Lezama, Marisol,Zú?iga-Villarreal, Noé
, p. 3223 - 3231 (2007/10/03)
The [Mn(CO)4-x(L){Ph2P(Se)NP(Se)Ph2-κ 2Se}] complexes, where x = 1 for L = PPh3 and PMePh2, and x = 2 for L = Ph2PCH2CH2PPh2 (diphos), were synth
Probing the electronic factors responsible for the cyclic electron-transfer induced isomerism fac ? mer: Synthesis, electrochemical and spectroscopic studies of fac-[Mn(CO)3(L′-L′)L] 0/+ complexes
Pereira, Cid,Ferreira, Heber G.,Schultz, Mario S.,Milanez, Juliana,Izidoro, Marta,Leme, Paulo C.,Santos, Regina H.A.,Gambardella, Maria Teresa P.,Castellano, Eduardo E.,Lima-Neto, Benedito S.,Carlos, Rose M.
, p. 3735 - 3744 (2008/10/09)
Spectroscopic (IR, 31P NMR and UV-Vis) and electrochemical studies on fac-[Mn(CO)3(L′-L′)(L)]0/+,where L′-L′ = 1,2-bis(diphenylphosphino)ethane (dppe) or 1,10-phenanthroline (phen) and L = bromide, triflate, imidazole (im), isonicotinamide (isn) or N-(2-hydroxyethyl)isonicotinamide (heisn), were undertaken to understand the effect of various ligands on the CO-Mn-L and CO-Mn-(L′-L′) bonding characteristics of these complexes. Crystal structures for L = triflate/L′-L′ = dppe, L = triflate/L′- L′ = phen and L = isn/L′-L′ = phen are reported and they show that the two Mn-O(OSO2CF3) and Mn-N(isn) distances are similar. The tricarbonyl complexes exhibit two major bands in the 250-300 and 350-450 nm region of the UV-Vis spectrum. The lowest energy bands have been assigned as a contribution from both the metal-centered (MC) and metal to ligand (dπ → L′-L′) charge transfer (MLCT) transitions. The energy of this maximum absorption decreases in the order Br- ～ triflate > im > isn ～ heisn. The cyclic four-component mechanism fac-Mn(I)→-efac-Mn(II)→mer-Mn(II)→+emer-Mn(I)→fac-Mn(I) was observed at room temperature by voltammetric techniques for all the cases. On the basis of d metal orbital splitting, an electronic molecular orbital diagram is proposed. In this model, the ligands along the z-axis play a relevant role in the reverse of the HOMO energies of the fac/mer isomers by stabilizing the metal dz2 orbital relative to dxy in mer-Mn(II).
Electron transfer and chemical reactions associated with the oxidation of an extensive series of mononuclear complexes [M(CO)2(k 1-P-P)(k2-P-P)X] and binuclear complexes [{M(CO) 2(k2-P-P)X}2
Bond, Alan M.,Colton, Ray,Van Den Bergen, Adrian,Walter, Jacky N.
, p. 3164 - 3176 (2008/10/09)
The electrochemical oxidation of extensive series of mononuclear and binuclear complexes was discussed. It was found that the synthesis of manganese and rhenium dicarbonyl halide with variety of diphosphene ligands was carried out. The manganese complexes
Phosphine, arsine and stibine complexes of manganese(I) carbonyl halides: Synthesis, multinuclear NMR spectroscopic studies, redox properties and crystal structures
Pope, Simon J. A.,Reid, Gillian
, p. 1615 - 1621 (2007/10/03)
Reaction of [Mn(CO)5X] (X = Cl or Br) with L-L {L-L = dppm (Ph2PCH2PPh2), dppe (Ph2PCH2CH2PPh2), dppp (Ph2PCH2CH2CH2PPh2), C6H4(PPh2)2-o, C6H4(PH2)2-o, dpae (Ph2AsCH2CH2AsPh2), diars [C6H4(AsMe2)2-o], dpsp (Ph2SbCH2CH2CH2SbPh2) or dmsp (Me2SbCH2CH2CH2SbMe2)} or with two molar equivalents of L (= PPh2H, PCy2H or PPhH2) in refluxing CHCl3 yielded the neutral manganese(I) complexes [MnX(CO)3(L-L)] and [MnX(CO)3L2] as yellow or orange solids. Infrared spectroscopic studies confirmed the fac-tricarbonyl arrangement and 1H, 13C-{1H}, 31P-{1H} and 55Mn NMR spectroscopy have been used to probe the solution behaviour. For a given halide 55Mn NMR spectroscopic studies showed some dependence of δ(55Mn) on halide, chelate ring size, substituent and donor atom. X-Ray crystallographic analyses on [MnCl(CO)3{C6H4(PPh2) 2-o}], [MnBr(CO)3(dppe)] and the diprimary phosphine complex [MnCl(CO)3{C6H4(PH2) 2-o}]·CH2Cl2 confirmed a fac-tricarbonyl arrangement, with the ditertiary or diprimary phosphine chelating. The structure of [MnBr(CO)3-(PPhH2)2] also shows a fac-tricarbonyl arrangement with the primary phosphine ligands mutually cis.
Preparation, reactions, and infrared spectra of fac-(CO) 3(P-P) Mn-Z complexes (P-P = DEPE, DPPE, DPPP; Z = H, OTs, OMe, OC(O) OMe, NCO, C1, Br, N3)
Li, Guang Qing,Orchin, Milton
, p. 43 - 47 (2007/10/03)
A series of new octahedral Mn(I) complexes fac(CO)3(depe)Mn-Z (depe = 1,2-bis(diethylphosphino)ethane, Z = H, OTs, OMe, OC(O)OMe, NCO, Cl, Br, N3) have been prepared and characterized, particularly with respect to their infrared spectra. The variations observed in the carbonyl stretching frequencies associated with the coordinated carbon monoxides are a function of the Z groups. Comparison of these spectra with similar spectra of the analogous dppp, 1,3-bis(diphenylphosphino)propane and dppe, 1,2-bis(diphenylphosphino)ethane complexes shows the effect of substituting phenyl groups for ethyl groups on the phosphorus atom. The depe azido complex (Z = N3) reacts with alkynes to give a triazolato complex which on hydrolysis with HCl liberates the triazole and regenerates the chloro complex from which the azido complex is made.
CATIONIC CARBONYL COMPLEXES OF MANGANESE(I) WITH DIPHOSPHINES
Carriedo, G. A.,Riera, V.
, p. 371 - 380 (2007/10/02)
The bromo-carbonyls fac-BrMn(CO)3(diphos)(diphos=Ph2P(CH2)nPPh2 for n=1(dpm), 2(dpe), 3(dpp) and 4(dbp)) react with AgClO4 in dichloromethane solution to give the neutral fac-O3ClOMn(CO)3(diphos).The reaction of the latter complexes at room temperature with a variety of ligands L=phosphines (PR3), phosphites P(OR)3), pyridine (Py), acetonitrile (MeCN), tetrahydrothiophene (THT) or acetone (Me2CO) leads to the cationic species fac-ClO4 (or to the ClO4, when L=CO).When L is a phosphorus ligand, the cationic fac-tricarbonyls isomerize upon heating to the mer isomers, which could only be isolated by this method for diphos=dpm, the reaction being accompanied by decomposition in the other cases.UV irradiation of the mer-ClO4 in the presence of a large excess of L gives the corresponding trans-ClO4.
