Thanks for the photos.
Two things to note, first the grey wire is already connected to neutral - a little bit poor, considering it is just hanging out loose, in the backbox of your existing stat.
Secondly, one of the brown zone valve wires has been trapped by the lid of the wiring centre - it shouldn't be an issue, but just make sure its clear of the lid before replacing it.
Next, it depends on what you want to acheive.
If you are happy with your single channel Hive receiver replacing the existing stat...
With the power safely isolated,
Connect the Brown wire to the L terminal of the Hive receiver backplate.
Connect the Grey wire to N.
Connect the Black wire to terminal 3
Put the Green/Yellow earth wire into Hives earth terminal.
Then add a short link wire between L and terminal 1.
Alternatively, for a neater finish, if you would like to put the Hive Receivers near to the wiring centre, we can guide you through the rewiring and decommissioning of your existing stats.