Substitution and derivatization reactions of a water soluble iron(ii) complex containing a self-assembled tetradentate phosphine ligand

Andrew D. Burrows, Deborah Dodds, Andrew S. Kirk, John P. Lowe, Mary F. Mahon, John E. Warren, Michael K. Whittlesey

    Research output: Contribution to journalArticlepeer-review

    Abstract

    Facile substitution reactions of the two water ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2)P{CH 2N(CH2P(CH2OH)2)CH2} 2P(CH2OH)}(H2O)2](SO4) (abbreviated to [Fe(L1)(H2O)2](SO4), 1) take place upon addition of Cl-, NCS-, N 3-, CO32- and CO to give [Fe(L 1)X2] (2, X = Cl; 4, X = NCS; 5, XN3), [Fe(L1)(κ2-O2CO)], 6 and [Fe(L 1)(CO)2](SO4), 7. The unsymmetrical mono-substituted intermediates [Fe(L1)(H2O)(CO)](SO 4) and [Fe(L1)(CO)(κ1-OSO3)] (8/9) have been identified spectroscopically en-route to 7. Treatment of 1 with acetic anhydride affords the acylated derivative [Fe{(AcOCH2) P{CH2N(CH2P(CH2OAc)2)CH 2}2P(CH2OAc)}(κ2-O 2SO2)] (abbreviated to [Fe(L2) (κ2-O2SO2)], 10), which has increased solubility over 1 in both organic solvents and water. Treatment of 1 with glycine does not lead to functionalisation of L1, but substitution of the aqua ligands occurs to form [Fe(L1)(NH2CH 2CO2-κ2N,O)](HSO4), 11. Compound 10 reacts with chloride to form [Fe(L2)Cl2] 12, and 12 reacts with CO in the presence of NaBPh4 to form [Fe(L 2)Cl(CO)](BPh4) 13b. Both of the chlorides in 12 are substituted on reaction with NCS- and N3- to form [Fe(L2)(NCS)2] 14 and [Fe(L2)(N 3)2] 15, respectively. Complexes 2·H2O, 4·2H2O, 5·0.812H2O, 6·1.7H 2O, 7·H2O, 10·1.3CH3C(O)CH 3, 12 and 15·0.5H2O have all been crystallographically characterised. © The Royal Society of Chemistry 2007.
    Original languageEnglish
    Pages (from-to)570-580
    Number of pages10
    JournalDalton Transactions
    Issue number5
    DOIs
    Publication statusPublished - 2007

    Keywords

    • AQUEOUS-SOLUTION
    • {AQUEOUS-SOLUTION
    • BENIGN
    • BUILDING-BLOCKS
    • {BUILDING-BLOCKS
    • CHEMISTRY
    • {CHEMISTRY
    • PLATINUM(II) COMPLEXES
    • NICKEL(II) COMPLEXES
    • RUTHENIUM
    • complexes
    • {COMPLEXES
    • IN-VITRO
    • HYDROGENATION
    • COORDINATION
    • {CRYSTAL-STRUCTURES
    • ENVIRONMENTALLY
    • ENVIRONMENTALLY} {BENIGN} {MEDIA
    • {ENVIRONMENTALLY} {BENIGN} {MEDIA
    • RAY CRYSTAL-STRUCTURES
    • {IN-VITRO
    • {MEDIA
    • NICKEL(II)
    • NICKEL(II)} {COMPLEXES
    • PLATINUM(II)
    • PLATINUM(II)} {COMPLEXES
    • RAY
    • RAY} {CRYSTAL-STRUCTURES

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