38148-37-7

Upstream product

• 14516-54-2 bromopentacarbonylmanganese(I) 
• 829-85-6 diphenylphosphane 
• 112137-88-9 MnBr(CO)4PH(C₆H₅)2 
• 87920-24-9 tributyl(penta-2,4-dienyl)stannane 
• 17154-34-6 (trimethylsilyl)diphenylphosphine 
• 38148-37-7 MnBr(CO)3(PH(C₆H₅)2)2 

Downstream Products

• 38148-37-7 MnBr(CO)3(PH(C₆H₅)2)2 

Relevant academic research and scientific papers

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.

Synthesis and structural characterization of the isomers of (1-phosphino-η3-pentenyl)tricarbonylmanganese

Diphenylphosphine reacts with η5-pentadienyltricarbonylmanganese (1) to give isomers Mn[P-(Ph)2CH2-η3-CHCHCHCH 3](CO)3 (2) and Mn[P(Ph)2CH2CH2-η3-CHCHCH 2](CO)3 (3). In both cases, phosphorus is added stereoselectively to the terminal carbon atom. Single-crystal X-ray diffraction studies of 2 and 3 confirm the unprecedented formation of the novel [1-(diphenylphosphino)-η3-pentenyl]tricarbonylmanganese complexes in which the phosphahexenyl ligand is bonded to the manganese center through an η3 interaction and also by phosphorus coordination affording six- and seven-membered pseudo -ring structures. Crystals of 2 are orthorhombic, space group Pna21 with a = 8.844 (1) A?, b = 16.806 (2) A?, c = 12.629 (1) A?, and Z = 4. The structure was refined to discrepancy indices of R = 0.0596 and Rw = 0.0602 for 1468 reflections having I > 3σ(I). Crystals of 3 are monoclinic, space group P21/a, with a = 10.630 (7) A?, b = 11.979 (8) A?, c = 14.27 (1) A?, β = 92.32 (6)°, and Z = 4. The structure was refined to discrepancy indices of R = 0.0641 and Rw = 0.0712 for 1735 reflections having I > 3σ(I). The two complexes have distorted-octahedral geometries with important differences both in lengths within the phosphino-η3-pentenyl systems and for the bonding parameters of the manganese ions. The metal carbonyl distances also show significant differences from one complex to the other. Monitoring of the reaction by IR and NMR (31P, 1H) spectroscopy showed that the addition of PHPh2 to 1 proceeds by initial conversion to 2 and subsequent formation of 3, with no evidence for preliminary interaction at either the manganese center or one of the CO carbon atoms. The reactions of cis-MnBr(CO)4PHPh2 (7a) and fac-MnBr-(CO)3(PHPh2)2 (8a) with C5H7SnBu3 to initially afford compound 2, are also discussed. The crystal of 7a is monoclinic, space group P21/c with a = 11.325 (5) A?, b = 10.342 (3) A?, c = 14.813 (5) A?, β = 95.08 (3)°, and Z = 4. The structure was refined to values of R = 0.0495 and Rw = 0.0540 for 2001 reflections with I > 3σ(I). The complex has a pseudooctahedral geometry with the bromine and diphenylphosphine ligands cis to each other.