TY - JOUR
T1 - Syntheses and structural characterizations of iron(II) complexes containing cyclic diphosphine ligands with positioned pendant nitrogen bases
AU - Jacobsen, George M.
AU - Shoemaker, Richard K.
AU - McNevin, Michael J.
AU - Dubois, M. Rakowski
AU - Dubois, Daniel L.
PY - 2007/9/24
Y1 - 2007/9/24
N2 - A series of new iron(II) complexes that contain cyclic diphosphine ligands with pendant amine bases, P2RN2 R′, have been synthesized and characterized (where P 2RN2R′ are substituted 1,5-diaza-3,7-diphosphacyclooctanes). These compounds include [Fe(P 2PhN2Ph)(CH3CN) 4](BF4)2 (5), cis-[Fe(P2 PhN2Ph)2(CH3-CN) 2](BF4)2 (6a), cis-[Fe(P2 PhN2Bz)2(CH3CN) 2](BF4)2 (6b), cis-[Fe(P2 CyN2Bz)2(CH3CN) 2](BF4)2 (6c), trans[HFe(P2 PhN2Ph)2(CH3CN)](BF 4) (7), and cis-Fe(P2PhN2 Ph)2(Cl)2 (8). The molecular structures of 5, 6b, and 7 have been confirmed by X-ray diffraction studies. For all complexes the cyclic diphosphine ligands contain one six-membered ring in a chair conformation and one six-membered ring in a boat conformation. For complex 7, the two rings that are in boat conformations result in N-H distances between the pendant amine nitrogens and the hydride ligand of 2.6 to 2.7 Å. Protonation of the pendant bases in complex 7 has been found to form several products. A structural assignment for a dominant protonated isomer has been assigned on the basis of 1H, 31P, and 15N NMR spectroscopic techniques.
AB - A series of new iron(II) complexes that contain cyclic diphosphine ligands with pendant amine bases, P2RN2 R′, have been synthesized and characterized (where P 2RN2R′ are substituted 1,5-diaza-3,7-diphosphacyclooctanes). These compounds include [Fe(P 2PhN2Ph)(CH3CN) 4](BF4)2 (5), cis-[Fe(P2 PhN2Ph)2(CH3-CN) 2](BF4)2 (6a), cis-[Fe(P2 PhN2Bz)2(CH3CN) 2](BF4)2 (6b), cis-[Fe(P2 CyN2Bz)2(CH3CN) 2](BF4)2 (6c), trans[HFe(P2 PhN2Ph)2(CH3CN)](BF 4) (7), and cis-Fe(P2PhN2 Ph)2(Cl)2 (8). The molecular structures of 5, 6b, and 7 have been confirmed by X-ray diffraction studies. For all complexes the cyclic diphosphine ligands contain one six-membered ring in a chair conformation and one six-membered ring in a boat conformation. For complex 7, the two rings that are in boat conformations result in N-H distances between the pendant amine nitrogens and the hydride ligand of 2.6 to 2.7 Å. Protonation of the pendant bases in complex 7 has been found to form several products. A structural assignment for a dominant protonated isomer has been assigned on the basis of 1H, 31P, and 15N NMR spectroscopic techniques.
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U2 - 10.1021/om700601h
DO - 10.1021/om700601h
M3 - Article
AN - SCOPUS:34948836881
VL - 26
SP - 5003
EP - 5009
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 20
ER -