Synthesis, characterization, and electrochemistry of a series of iron(II) complexes containing self-assembled 1,5-Diaza-3,7-diphosphabicyclo 3.3.1 nonane Ligands
Burrows, A. D., Harrington, R. W., Kirk, A. S., Mahon, M. F., Marken, F., Warren, J. E. and Whittlesey, M. K., 2009. Synthesis, characterization, and electrochemistry of a series of iron(II) complexes containing self-assembled 1,5-Diaza-3,7-diphosphabicyclo 3.3.1 nonane Ligands. Inorganic Chemistry, 48 (20), pp. 9924-9935.
Related documents:This repository does not currently have the full-text of this item.
You may be able to access a copy if URLs are provided below. (Contact Author)
The reaction between PPh(CH2OH)(2), iron(II) sulfate, ammonium sulfate, and formaldehyde in aqueous solution gives the iron(II) complex [Fe(kappa(2)-O2SO2)L-2] (1), where L is the bidentate phosphine ligand 3,7-diphenyl-1,5-diaza-3, 7-diphosphabicyclo[3.3.1]nonane. During the course of the reaction, the ligand L self-assembles on the metal center. The reaction between PPh(CH2OH)(2), iron(II) chloride, ammonium chloride, and formaldehyde under similar conditions gives cis[FeCl2L2] (cis-2). The complex cis-2 is converted into trans-2 in Et2O, whereas in water it is converted into cis-[Fe(OH2)(2)L-2](2+), though both of these interconversions are reversible. The chloro ligands in cis-2 are readily displaced by reaction with thiocyanate, azide, and carbonate to give cis- and trans-[Fe(NCS)(2)L-2] (cis- and trans-3), cis- and trans-[Fe(N-3)(2)L-2] (cis- and trans-4), and [Fe(kappa(2)-O2CO)L-2] (5), respectively. The complex cis-2 reacts with CO in water to give trans-[FeCl(CO)L-2]Cl (trans-6), whereas trans-2 reacts with CO in diethyl ether to give cis-[FeCl(CO)L-2]Cl (cis-6), though cis-6 isomerizes in water to form trans-6. The reaction of cis-2 with sodium borohydride gives the hydride chloride complex trans-[FeCl(H)L-2] (7). Electrochemical studies have been undertaken on complexes 1, cis-2, and 7. These reveal reversible oxidations for cis-2 and 7, with the latter giving rise to an unusual 17-electron iron(III) hydride chloride complex. Crystal structures have been obtained for 1, trans-2, trans-3, 5, and 7.
|Creators||Burrows, A. D., Harrington, R. W., Kirk, A. S., Mahon, M. F., Marken, F., Warren, J. E. and Whittlesey, M. K.|
|Departments||Faculty of Science > Chemistry|
Actions (login required)