78251-33-9

Upstream product

• 14516-54-2 bromopentacarbonylmanganese(I) 
• 6737-42-4 1,3-bis-(diphenylphosphino)propane 
• 148447-53-4 fac-tricarbonyl(1,3-bis(diphenylphosphino)propane)hydridomanganese(I) 
• 10035-10-6 hydrogen bromide 

Downstream Products

• 191719-65-0 fac-Mn(CO)3(1,3-bis(diphenylphosphino)propane)(N₃) 
• 1250872-08-2 Mn(1,3-bis(diphenylphosphino)propane)(bis(diphenylphosphino)methane)(CO)(Br) 
• 78099-97-5 fac-O₃ClOMn(CO)3(dpp) 
• 145088-69-3 {Mn(CO)4(C₆H₅)2P(CH₂)3P(C₆H₅)2}⁽¹⁺⁾*BF₄^(1-)={Mn(CO)4((C₆H₅)2P(CH₂)3P(C₆H₅)2)}(BF₄) 

Relevant academic research and scientific papers

Synthesis, structures, and reactions of manganese complexes containing diphosphine ligands with pendant amines

Addition of the pendant amine ligand PNRP (PNRP = Ph2PCH2NRCH2PPh2; R = Me, Ph, n-Bu) to Mn(CO)5Br gives fac-Mn(PNRP)(CO)3Br. Photolysis of fac-Mn(PNRP)(CO)3Br with dppm [dppm = 1,2-bis(diphenylphosphino)methane] provides mixed bis(diphosphine) complexes, trans-Mn(PNRP)(dppm)(CO)(Br). Reaction of trans-Mn(PN RP)(dppm)(CO)(Br) with LiAlH4 leads to trans-Mn(PN RP)(dppm)(CO)(H), which has been characterized by crystallography. Mn(P2PhN2Bn)(dppm)(CO)(H) [P 2PhN2Bn = 1,5-diphenyl-3,7-dibenzyl- 1,5-diaza-3,7-diphosphacyclooctane] can be prepared in a similar manner; its structure has one chelate ring in a chair conformation and the second in a boat conformation. The boat-conformer ring directs the nitrogen of the ring toward the carbonyl ligand, and the N...C distance between one N of the P 2PhN2Bn ligand and CO is 3.171(4) A, indicating a weak interaction between the N of the pendant amine and the CO ligand. Reaction of NaBArF4 (ArF = 3,5-bis(trifluoromethyl)phenyl) with Mn(P-P)(dppm)(CO)(Br) produces the cations [Mn(P-P)(dppm)(CO)]+. The crystal structure of [Mn(PN MeP)(dppm)(CO)][BArF4] shows two very weak agostic interactions between C-H bonds on the phenyl ring and the Mn. The cationic complexes [Mn(P-P)(dppm)(CO)]+ react with H2 to form dihydrogen complexes [Mn(H2)(P-P)(dppm)(CO)]+ (K eq = 1-90 atm-1 in fluorobenzene, for a series of different P-P ligands). Similar equilibria with N2 produce [Mn(N 2)(P-P)(dppm)(CO)]+ (Keq generally 1-3.5 atm-1 in fluorobenzene).

Structural characterization of several (CO)3(dppp)MnX derivatives, dppp = 1,3-bis(diphenylphosphino)propane and X = H, OTs, OC 2H5, Cl, Br, or N3. An assessment of their efficacy for catalyzing the coupling of carbon dioxide and epoxides

The X-ray structures of a series of (CO)3(dppp)MnX complexes, X = H, OTs, OEt, Cl, Br, and N3, and dppp = 1,3-bis(diphenylphosphino)propane, prepared by literature methods are reported. Several of these derivatives have been examined for their ability to serve as catalysts for the coupling of cyclohexene oxide and carbon dioxide. Although, these organometallic complexes do catalyze the formation of polycarbonate, their activity is not competitive with other very effective catalysts for this coupling reaction. Nevertheless, findings from these studies contribute significantly to our understanding of this important process. The complex containing the alkoxide ligand is the most active, yet it possesses a TON (mol epoxide consumed/mol Mn) of only 50 for a 24 h reaction. In this instance the (CO)3(dppp)MnOEt complex exists as the carbonate species, (CO) 3(dppp)MnOC(O)OEt, because of rapid CO2 insertion into the Mn-OEt bond. The order of epoxide ring-opening by the X group (initiator) was found to be -OC(O)OR > Cl ≥ N3 > Br. Furthermore, since these complexes are substitutionally inert, this process is best defined as occurring via an associative interchange process and is rate-limiting.

Phosphine, arsine and stibine complexes of manganese(I) carbonyl halides: Synthesis, multinuclear NMR spectroscopic studies, redox properties and crystal structures

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)

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.