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From the Guardian...
Why is Salmond going now? He has been saying for weeks when asked if he planned to resign in the event of losing the referendum vote, he would complete his term as first minister, which would take him to the next Scottish election in 2016.
So why now? He may already have had a deal in place with Sturgeon depending on the referendum result. He may have judged, as he suggested in his resignation speech, that she is capable of reaching the parts of the electorate immune to his charms, primarily women, and also someone younger to consolidate and build on the enthusiasm of all those new young recruits.