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


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Burrows, A. D., Dodds, D., Kirk, A. S., Lowe, J. P., Mahon, M. F., Warren, J. E. and Whittlesey, M. K., 2007. Substitution and derivatization reactions of a water soluble iron(II) complex containing a self-assembled tetradentate phosphine ligand. Dalton Transactions

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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.

Details

Item Type Articles
CreatorsBurrows, A. D., Dodds, D., Kirk, A. S., Lowe, J. P., Mahon, M. F., Warren, J. E. and Whittlesey, M. K.
Uncontrolled Keywordspseudohalide, 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
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code4620

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