1552316-86-5Relevant academic research and scientific papers
Reactions of the σ,π-furyl complex [Fe2(CO) 6(μ-Fu)(μ-PFu2)] (Fu = C4H3O) with phosphines: Carbonyl substitution, migratory carbonyl insertion and cyclometallation-induced furan elimination
Rahaman, Ahibur,Alam, Fakir Rafiqul,Ghosh, Shishir,Tocher, Derek A.,Haukka, Matti,Kabir, Shariff E.,Nordlander, Ebbe,Hogarth, Graeme
, p. 326 - 335 (2014)
The reactivity of the σ,π-furyl complex [Fe2(CO) 6(m-Fu)(μ-PFu2)] (1) towards PPh3 and a range of bidentate phosphines has been studied and a number of different reaction products have been identified. With PPh3, carbonyl substitution affords [Fe2(CO)5(PPh3)(μ-Fu) (m-PFu2)] (2) in which the new phosphine is coordinated to the iron center that is σ-coordinated by the bridging furyl moiety. With small bite-angle diphosphines - bis(diphenylphosphino)methane (dppm) and 1,8-bis(diphenylphosphino)naphthalene (dppn) - carbonyl substitution and migratory carbonyl insertion result to give the furyleacyl complexes with bridging, [Fe2(CO)4(μ-dppm)(m-O=C-Fu)(μ-PFu 2)] (3), or chelating, [Fe2(CO)4(κ 2-dppn)(μ=OCeFu)(μ-PFu2)] (4), diphosphines, respectively. With the more flexible diphosphines Ph2P(CH 2)nPPh2 (n = 2, dppe, n = 3, dppp), the cyclometallated products [Fe2(CO)5{μ, κ2-C6H4PPh(CH2) nPPh2}(μ-PFu2)] (n = 2, 5; n = 3, 6) are isolated as a result of carbonyl substitution and furan elimination, and a similar complex [Fe2(CO)5{μ,κ2-C 6H4PPh(C6H4)PPh2}(μ- PFu2)] (7) is generated from the more rigid diphosphine bis(diphenylphosphino) benzene (dppb). With bis(diphenylphosphino)-1,1- binaphthalene (1,1-BINAP) the novel tridentate phosphine complex [Fe 2(CO)5{μ,κ3-C6H 4P(C20H12PPh2)C6H 4PFu}] (8) results from the putative coupling of cyclometallated diphosphine and difurylphosphido ligands, following elimination of two equivalents of furan. The crystal structures of 2, 3, 5 and 8 have been determined and allow a detailed insight into the overall reaction profile.
