Paramagnetic NMR

The review covers the primary refereed literature and scholarly review articles between June, 2002, and May, 2004. Patent applications, meeting abstracts and dissertations are not included. 

---

However, it was pointed out that two other observations are out of line with the iron(I) formulation and more consistent with an iron(II)-porphyrin radical anion [290] (1) the low-intensity red-shifted Soret band in the UV-VIS spectrum with broad maxima in the a,(3-region compared to, for instance, Fe(TPP) in THF, is typical of a porphyrin radical, and (2) the bond lengths of the porphyrin core indicate population of the (antibonding) LUMO of the ligand (i.e., the presence of an extra electron in the re-system). The presence of porphyrin radical character in the electronic ground state was also inferred from the paramagnetic NMR-shifts of the pyrrole protons at the meso and p-carbon atoms [291]. 

By far the most NMR studies have been concerned with the amine adducts of Ni(R-dtp)2 complexes. The green complexes formed with primary (mono-and bidentate) and heterocyclic (mono- und bidentate) amines and the yellow-brown five-co-ordinate adducts with secondly amines exhibit paramagnetic shifts in their NMR spectra. The use of paramagnetic NMR shifts in mapping unpaired electron spin distributions of paramagnetic complexes has been reviewed 378-381) jhe upfield paramagnetic shifts of NH protons are diagnostic... 

A review has been given on paramagnetic resonance spectroscopy of metal centers. It comprises both paramagnetic NMR as well as high frequency EPR methods applied mostly to copper proteins of the blue type but also to iron and manganese containing proteins.42... 

If an MU1 acetylaoetonate is used for the porphyrin metallation, Min(Por)(acac) is formed, in which the acetylacetonato coordinates to the metal as a bidentate ligand (Scheme 7).1703 The paramagnetic NMR shift of the phenyl proton in Euni(TPP)(acac) suggests a large displacement of the europium atom from the centre of the porphyrin ( 2.0 A) with long Eu—Np r bonds ( 2.83 A). Sandwich complexes Ce(TPP)2 and PrH(TTP)2 have been reported.34... 

PARAMAGNETIC NMR LANTHANIDE INDUCED SHIFTS FOR EXTRACTING SOLUTION STRUCTURES... 

---