Hydride complexes [FeH(N-N)P3]BPh4 (1, 2) [N-N = 2,2‘-bipyridine (bpy) and 1,10-phenanthroline (phen); P = P(OEt)3, PPh(OEt)2, and PPh2OEt] were prepared by allowing FeCl2(N-N) to react with phosphite in the presence of NaBH4. The hydrides [FeH(bpy)2P]BPh4 (3) [P = P(OEt)3 and PPh(OEt)2] were prepared by reacting the tris(2,2‘-bipyridine) [Fe(bpy)3]Cl2·5H2O complex with the appropriate phosphite in the presence of NaBH4. The protonation reaction of 1 and 2 with acid was studied and led to thermally unstable (above −20 °C) dihydrogen [Fe(η2-H2)(N-N)P3]2+ (4, 5) derivatives. The presence of the H2 ligand is indicated by short T1min values (3.1−3.6 ms) and by JHD measurements (31.2−32.5 Hz) of the partially deuterated derivatives. Carbonyl [Fe(CO)(bpy){P(OEt)3}3](BPh4)2 (6) and nitrile [Fe(CH3CN)(N-N)P3](BPh4)2 (7, 8) [N-N = bpy, phen; P = P(OEt)3 and PPh(OEt)2] complexes were prepared by substituting the H2 ligand in the η2-H2 4, 5 derivatives. Aryldiazene complexes [Fe(ArN=NH)(N-N)P3](BPh4)2 (9, 10, 11) (Ar = C6H5, 4-CH3C6H4) were also obtained by allowing hydride [FeH(N-N)P3]BPh4 derivatives to react with aryldiazonium cations in CH2Cl2 at low temperature.

Preparation and Reactivity of Mixed-Ligand Iron(II) Hydride Complexes with Phosphites and Polypyridyls

ALBERTIN, Gabriele;ANTONIUTTI, Stefano;BORTOLUZZI, Marco
2004-01-01

Abstract

Hydride complexes [FeH(N-N)P3]BPh4 (1, 2) [N-N = 2,2‘-bipyridine (bpy) and 1,10-phenanthroline (phen); P = P(OEt)3, PPh(OEt)2, and PPh2OEt] were prepared by allowing FeCl2(N-N) to react with phosphite in the presence of NaBH4. The hydrides [FeH(bpy)2P]BPh4 (3) [P = P(OEt)3 and PPh(OEt)2] were prepared by reacting the tris(2,2‘-bipyridine) [Fe(bpy)3]Cl2·5H2O complex with the appropriate phosphite in the presence of NaBH4. The protonation reaction of 1 and 2 with acid was studied and led to thermally unstable (above −20 °C) dihydrogen [Fe(η2-H2)(N-N)P3]2+ (4, 5) derivatives. The presence of the H2 ligand is indicated by short T1min values (3.1−3.6 ms) and by JHD measurements (31.2−32.5 Hz) of the partially deuterated derivatives. Carbonyl [Fe(CO)(bpy){P(OEt)3}3](BPh4)2 (6) and nitrile [Fe(CH3CN)(N-N)P3](BPh4)2 (7, 8) [N-N = bpy, phen; P = P(OEt)3 and PPh(OEt)2] complexes were prepared by substituting the H2 ligand in the η2-H2 4, 5 derivatives. Aryldiazene complexes [Fe(ArN=NH)(N-N)P3](BPh4)2 (9, 10, 11) (Ar = C6H5, 4-CH3C6H4) were also obtained by allowing hydride [FeH(N-N)P3]BPh4 derivatives to react with aryldiazonium cations in CH2Cl2 at low temperature.
2004
43
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10278/27781
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