Nitrosyl questions

1. What can be deduced about the mode of bonding of the NO ligand from stretching
NO wavenumbers in the attached IR spectra of the Ni and Fe nitrosyl complexes
prepared in this Part 2?

In the Ni complex, the NO has a wavenumber at 1725 cm-1 while in the Fe complex, the NO
has a wavenumber of 1685 cm-1. In accordance with equation x, it would be fair to assume
that the ligand in the Ni complex is closer to a double bonded N=O group (as the force
constant would be stronger). Therefore, the ligand in the Fe complex is closer to a single
bonded N-O group as the force constant is weaker, therefore indicating a longer/weaker
bond between N and O.

2. Discuss the possible oxidation states of the metal in the 2 complexes. Which
geometry does the Nickel centre adopt in [NiBr(NO)(PPh3)2]? Compare with parent
[NiBr2(PPh3)2].

Ox state of Ni – 2+
Ox state of Fe – 3+
Ox state of Ni in parent – 2+
- Determine the g value from the field position (H, in milliTesla) of the central line of
the ESR signal of the complex [Fe(NO)(S2CNEt2)2] in CHCl3, using conveniently DPPH
radical as standard.
G = 1.9692
- Determine the isotropic a(N) value from the recorded ESR spectrum of
[Fe(NO)(S2CNEt2)2] showing a 14N triplet, and convert it to frequency units, using the
equation in manual.

- What can you say about your Fe nitrosyl complex from its g-value?
- Calculate by direct ratio of the coupling constants the percentage probability of
finding an unpaired electron on Nitrogen in your molecule. What does this value tell
you about the electronic structure of iron complex, in combination with the
conclusion from the IR spectroscopy and metal oxidation state.