FLUXIONALITY

I.

Ring Whizzing

3 1H NMR resonances are seen at low T (AABB multiplet for the 4 olefinic protons at 66.5ppm, a singlet for the 5-Cp ring at 3-3.5ppm, and another for the C1 proton)
only 2 singlets of almost equal intesntiy are seen at room T => ring whizzing of the 1-Cp
ring around Fe

not because of dissociation + recombination

1,2 or 1,3-shifts

II.

the indenyl system would rearrange rapidly if a direct 1,3-shift occurs via a 3-allyl
intermediate or transition state
a direct 1,2-shift would be suppressed in the indenyl system since it would have to go
through a high energy o-xylene intermediate
therefore, if the molecule is fluxional, it would do so via the 1,3 process; however, the
molecule is nonfluxional, which means that the 1,2-shift is the pathway for the 1-Cp
rings fluxionality

Interchange of 1-Cp and 5-Cp Rings

at low T, 2 sharp singlets are observed at 5.9ppm and 5.2ppm; both broaden when T is
increased => the two 1-Cp rings undergo ring whizzing to give 1 peak and the 5-Cp ring
gives the other peak
at high T, only 1 sharp singlet is observed => the 5-Cp and 1-Cp rings are exchanging
the molecule can undergo 5-Cp and 1-Cp ring exchange because it is coordinately
unsaturated (16e) => does not occur in 18e complexes

the exchange is also observed when one of the ligands in the complex has the ability to
shuttle between two structures having a difference of 2 electrons (such as NO)

III.
Allyl Complexes
- anti protons (1-3ppm) are closer to the metal => shielded and high field relative to the
syn (2-5ppm) protons; the proton at the middle is at 4-6.5ppm
- since the molecule is rigid, the 3 types of protons produce distinctive chemical shifts
- the syn and anti protons do not couple with each other but couple with the proton on the
central carbon => the syn and anti protons appear as doublets while the central proton
appears at a multiplet
- upon raising the temperature, the two doublets collapse into one and the multiplet
becomes a quintet => only 2 types of protons (4 terminal and 1 nonterminal hydrogen)

IV.
-

Allene Complexes
3 signals : the lowest value is for the a and b protons while the highest is for the c proton
the coupling constant between a and b is smaller than in free allene
4 signals may be observed if the symmetry is lower

V.
Scrambling of CO groups
- the interconversion of permutational isomers and geometric isomers in mononuclear
complexes (example: Fe(CO)5)
- the interconversion of bridging and terminal arrangements and the migration and
scrambling of CO groups in binuclear and polynuclear complexes => arises because the
energy of the M2(CO)2 system does not vary much over an entire range of configurations

2 signals at low T (cis, trans) and 1 signal at R.T => interconversion between the cis and
trans forms at R.T

the cis/trans interconversion results in an overall exchange of bridging and terminal CO

groups

the bridging COs are inequivalent because one is cis to Cp and one is cis to CO; the
terminal CO should appear as a doublet since it is coupled to one Rh; the bridging CO
should appear as a triplet since they are coupled to two Rh atoms