So I had a go at this this afternoon but without success.
Changed the handler on the TBK to Wave-Tweaker and can check settings and set up the switch.
Identified in the switch I want to control as having an ID of DEF7
Identified the group I want to use (has the correct function) from the manual as group 4
So using the Wave-tweaker set the Associated Group ID: 4
and the Associated Group Members: DEF4
and Command Class: Auto-Detect
Saved that and SYNED turned green fine, however the second switch did not start controller the Z-Wave device.
Instead the Left TBK switch in the Smartthings GUI became detached from the physical switch and right switch started controlling that, so a step back I think. I am more confused than ever on what setting I should put in with the Wave-tweaker.