Wydział Chemii

Natasza Sprutta

S. P. Rath

Marylin M. Olmstead

Alan L. Balch

2005

Inorganic Chemistry

44

1452-1459

10.1021/ic0486623

Naukowa

Angielski

Artykuł

The crystal structures of meso-NH₂−OEPH₂, Ni^II(meso-NH₂−OEP), and Cu^II(meso-NH₂−OEP) (where OEP is the dianion of meso-amino-octaethylporphyrin) have been determined to examine the effects of the meso-substituent on the geometry of the ligand. Cu^II(meso-NH₂−OEP) has a nearly planar geometry while the free ligand itself and Ni^II(meso-NH₂−OEP) have ruf conformations. Ni^II(meso-NH₂−OEP) is much less reactive toward oxidation than are (py)₂Fe^II(meso-NH₂−OEP), ClFe^III(meso-NH₂−OEP), or Ni^II(meso-HO−OEP), which all undergo oxidation in pyridine solution when exposed to dioxygen. Treatment of Ni^II(meso-NH₂−OEP) with iron(III) chloride in chloroform solution does result in oxidation of the ligand in two separate processes. One involves oxygenation at the trans-meso position, while the other results in ring cleavage and removal of the amino function. The open-chain tetrapyrrole complex, Ni^II(OEB−CO₂Et), has been characterized by single-crystal X-ray diffraction and shown to contain a helical ligand with a four-coordinate nickel ion.

https://doi.org/10.1021/ic0486623

https://www.acs.org/content/acs/en.html