| 17225909 |
Burrows AD, Dodds D, Kirk AS, Lowe JP, Mahon MF, Warren JE, Whittlesey MK: Substitution and derivatization reactions of a water soluble iron (II) complex containing a self-assembled tetradentate phosphine ligand. Dalton Trans. 2007 Feb 7;(5):570-80. Epub 2006 Dec 22.
Facile substitution reactions of the two water ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2) P{CH2N (CH2P (CH2OH) 2) CH2}2P (CH2OH)}(H2O) 2](SO4) (abbreviated to [Fe (L1)(H2O) 2](SO4), 1) take place upon addition of Cl-, NCS-, N3 (-), CO3 (2-) and CO to give [Fe (L1) X2] (2, X = Cl; 4, X = NCS; 5, X=N3), [Fe (L1)(kappa2-O (2) CO)], 6 and [Fe (L1)(CO) 2](SO4), 7. The unsymmetrical mono-substituted intermediates [Fe (L1)(H2O)(CO)](SO (4)) and [Fe (L (1))(CO)(kappa (1)-OSO (3))] (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) CH2}2P (CH2OAc)}(kappa2-O (2) SO2)] (abbreviated to [Fe (L2)(kappa2-O (2) SO2)], 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 (L (1))(NH (2) CH (2) CO (2)-kappa (2) N,O)](HSO (4)), 11. Compound 10 reacts with chloride to form [Fe (L (2)) Cl (2)] 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, respectively. 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 crystallographically characterised. |
1(0,0,0,1) |