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Molecular boxes

OK a bit more about prussian blue and what are known as coordination polymers. The idea of a coordination polymer is that it is a repeating network where bridging ligands link each metal centre to the next, thus making a polymer.

To understand them we need to build up to it, it is not a good idea to try to run before you walk. Lets start with a metal complex which has lone pairs poking out into space ready to bind to something else. Err Oh Err how about [CpFe(PR3)(CN)2]this is a 18 VE complex. For those of you who do not know what the 18 VE rule is then I suggest that you read Tony Hill‘s book which will explain the 18 VE rule. A copy of organotransition metal chemistry by Anthony Hill can be obtained from the RSC.

Here is a picture of the anion, you can see it has the two nitrile groups which each have a lone pair on the nitrogen atom.

The cyclopentadienyl iron triphenylphosphine dicyanide anion

Now here is a complex where the Cu(PCy3) group is used, this group is a weak lewis acid so it has the ability to bind to lewis bases such as the lone pairs of the cyanide groups of the iron fragment.

You can now see the square-ish arrangement of two copper atoms (green) and two irons (yellow), what you are looking at may be a bit of an “atomic fog” but do not worry yourselves too much.

The diiron dicopper square complex

As I feel kind here is a picture of the inner core of the complex, I have removed the carbon groups attached to the phosphorus atoms.

Copper iron square complex without some of the groups to give you a better look

Now if we use three cyanides to link a metal to three other metals we can make a cube, well it is a bit of a distorted cube. I am sure that the more able minded persons reading this can understand how this is step towards a infinite solid with lots of cubes in it. Here is a picture of it. Before you ask the cage is anionic, and the atom at the centre of the cage is a potassium. This complex was published by T.B.Rauchfuss in the Journal of the American Chemical Society, 2007, 129, 1931.

The cube of eight cobalt atoms bridged by 12 cyanide ligands

The cube is capped with cyclopentadienyl and tetramethylcyclobutadiene ligands. For those of you who can not see through the atomic soup (or atomic fog) here is the cube without the capping ligands.

The cobalt cage without the capping groups

* If as a university teacher you do not get on with Tony Hill’s book then you can always replace this with another book.


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