My understanding from other places is that:
The NHS site will only allow you to book if you are actually eligible. If you are given a slot online when you try, but haven't received your letter, that just means the system is ahead of the letter getting to you. You're eligible and it's ok. If you are not given a slot, then you are simply not yet eligible. Try tomorrow.
So book if you can, it's what they want you to do. The bit on the front page that says "You can only use this service if you have received a letter inviting you to book your vaccination appointments" isn't actually so.
www.nhs.uk/conditions/coronavirus-covid-19/coronavirus-vaccination/book-coronavirus-vaccination/
As we are in group 6 and not yet eligible, I've not tried, and I emphasise, the above is only my understanding of the situation.
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