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 journalArticle

11 Citations (Scopus)

Abstract

Facile substitution reactions of the two H2O ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2)P{CH2N(CH2P(CH2OH)2)CH2}2P(CH2OH)}(H2O)2](SO4) ([Fe(L1)(H2O)2](SO4), 1) take place upon addn. of Cl-, NCS-, N3-, CO32- and CO to give [Fe(L1)X2] (2, X = Cl; 4, X = NCS; 5, X:N3), [Fe(L1)(k2-O2CO)] (6), and [Fe(L1)(CO)2](SO4) (7). The unsym. mono-substituted intermediates [Fe(L1)(H2O)(CO)](SO4) (8) and [Fe(L1)(CO)(k1-OSO3)] (9) were identified spectroscopically en-route to 7. Treatment of 1 with acetic anhydride affords the acylated deriv. [Fe{(AcOCH2)P{CH2N(CH2P(CH2OAc)2)CH2}2P(CH2OAc)}(k2-O2SO2)] ([Fe(L2)(k2-O2SO2)], 10), which has increased soly. over 1 in both org. solvents and H2O. Treatment of 1 with glycine does not lead to functionalization of L1, but substitution of the aqua ligands occurs to form [Fe(L1)(NH2CH2CO2-k2N,O)](HSO4) (11). Compd. 10 reacts with chloride to form [Fe(L2)Cl2] (12), and 12 reacts with CO in the presence of NaBPh4 to form [Fe(L2)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)(N3)2] (15), resp. Complexes 2.H2O, 4.2H2O, 5.0.812H2O, 6.1.7H2O, 7.H2O, 10.1.3CH3C(O)CH3, 12 and 15.0.5H2O have all been crystallog. characterized.
Original languageEnglish
Pages (from-to)570-580
Number of pages11
JournalDalton Transactions
Issue number5
Publication statusPublished - 2007

Keywords

  • pseudohalide
  • crystal structure iron hydroxymethylphosphinomethyl diazadiphosphacyclooctane halide pseudohalide glycinato carbonyl
  • N'-bis[bis(hydroxymethyl)phosphinomethyl]diazadiphosphacyclooctane complexes with halide
  • iron aqua hydroxymethylphosphinomethyl diazadiphosphacyclooctane hydrophilic coordinative substitution
  • Crystal structure
  • glycine
  • N'-bis[bis(hydroxymethyl)phosphinomethyl]diazadiphosphacyclooctane aqua complex with halide
  • Substitution reaction (of iron(II) N
  • and carbonyl)
  • and carbonyl ligands and O-acetylated deriv.)
  • Molecular structure (of iron(II) N

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