This tutorial is another problem-type question, again involving the application of electron
counting rules in determining the structure of organometallic compounds. The ligand (C3O2)
is not one you are likely to have come across, but it is sufficiently similar to one's that you
are familiar with that you can extrapolate properties.
1. The oxide of carbon C3O2, carbon suboxide, is the anhydride of malonic acid and can
easily be made by dehydration of this acid. It has the linear structure O=C=C=C=O. The
reaction of carbon suboxide with Ni(C2H4) (PPh3)2 afforded a yellow-green solid A. This
contains Ni, 9.01%; P, 9.51%, Ο, 4.91%; C, 71.91%; H, 4.65% and shows two strong
stretches in the v (CO) region at 1773 and 2086 cm-1. The 31P (1H decoupled) NMR
spectrum shows two signals of equal intensity at 8 24.8 and 43.6, while the 13C (1H
decoupled) NMR spectrum showed three signals, a doublet at 8 -12.3, a singlet at 8
157.7 and a doublet at 8 187.8, as well as signals in the phenyl region.
(i) Show (with structural drawings) all the possible ways in which the carbon suboxide
molecule could coordinate to a metal centre. Note that the C=C double bonds can act as
olefinic bonds (clue revise how olefins can bind to transition metals, i.e. Zeise's salt).
For all of your possible structures, indicate which has equivalent or inequivalent
phosphine groups (i.e. consider the 3D-arrangement of ligands carefully).
(ii) Using the information obtained in part (i) and the NMR data given above, decide what
is the structure of compound A. You may find it useful to know that carbon suboxide
shows two signals in the 13C spectrum at 8 -14.62 and 129.7 in the intensity ratio 1:2.
Assign as far as you can all the NMR data
(ii) What is the oxidation state of the Ni atom in compound A? Hence decide on the d-
electron count and the total number of valence electrons. Are these values normal for
nickel?