Albertin Gabriele, Antoniutti Stefano, Bortoluzzi Marco
Dipartimento di Chimica, Università Ca' Foscari di Venezia, Dorsoduro, 2137, 30123 Venezia, Italy.
Inorg Chem. 2004 Feb 23;43(4):1328-35. doi: 10.1021/ic0348190.
Hydride complexes [FeH(N-N)P3]BPh4 (1, 2) [N-N = 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen); P = P(OEt)4, 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 degrees C) dihydrogen [Fe(eta2-H2)(N-N)P3]2+ (4, 5) derivatives. The presence of the H2 ligand is indicated by short T(1 min) values (3.1-3.6 ms) and by J(HD) measurements (31.2-32.5 Hz) of the partially deuterated derivatives. Carbonyl Fe(CO)(bpy)[P(OEt)3]32 (6) and nitrile Fe(CH3CN)(N-N)P32 (7, 8) [N-N = bpy, phen; P = P(OEt)3 and PPh(OEt)2] complexes were prepared by substituting the H2 ligand in the eta2-H2 4, 5 derivatives. Aryldiazene complexes Fe(ArN=NH)(N-N)P32 (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.
通过使FeCl2(N-N)在NaBH4存在下与亚磷酸酯反应，制备了氢化物配合物[FeH(N-N)P3]BPh4（1, 2）[N-N = 2,2'-联吡啶（bpy）和1,10-菲咯啉（phen）；P = P(OEt)4、PPh(OEt)2和PPh2OEt]。通过使三（2,2'-联吡啶）[Fe(bpy)3]Cl2·5H2O配合物在NaBH4存在下与适当的亚磷酸酯反应，制备了氢化物[FeH(bpy)2P]BPh4（3）[P = P(OEt)3和PPh(OEt)2]。研究了1和2与酸的质子化反应，得到了热不稳定的（高于-20℃）二氢[Fe(η2-H2)(N-N)P3]2+（4, 5）衍生物。部分氘代衍生物的短T(1 min)值（3.1 - 3.6 ms）和J(HD)测量值（31.2 - 32.5 Hz）表明了H2配体的存在。通过在η2-H2 4, 5衍生物中取代H2配体，制备了羰基Fe(CO)(bpy)[P(OEt)3]32（6）和腈Fe(CH3CN)(N-N)P32（7, 8）[N-N = bpy, phen；P = P(OEt)3和PPh(OEt)2]配合物。芳基重氮配合物Fe(ArN=NH)(N-N)P32（9, 10, 11）（Ar = C6H5, 4-CH3C6H4）也通过使氢化物[FeH(N-N)P3]BPh4衍生物在低温下于CH2Cl2中与芳基重氮阳离子反应得到。
