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@nneil
The link pin is different from the rest. It doesn't have a dimple and is a different colour. The powerlink is a SRAM proprietary feature they got when they bought Sedis/Sachs. That's why I use SRAM.
You have to do it right, but there are many different rules depending on your chain:
http://www.shimano.com/publish/content/global_cycle/en/us/index/tech_support/tech_tips.download.-Par50rparsys-0030-downloadFile.html/03)%20Chain%20Installation.pdf