Hi Matchless, hope all well with you? Sorry I can't contact you directly as my pm has been removed on this forum.
On the issue of putting a lever valve on the hot outlet, that would be fine on an unvented cylinder, as outlet is closed when taps are closed anyhow, although pipework volume would be larger obviously when valve open or not installed. The wrong place is if the pressure relief valve and/or any expansion vessel serving the unvented unit is isolated with a valve.
Unvented units just need their expansion, pressure relief, and T&P valve to be unimpeded.
Think of it this way, - You could install an unvented unit that has nothing else but one tap to supply just a metre of pipe away from hot outlet of unit. Nothing wrong with that at all, because the unit still has its expansion and safety valves etc.
Although a valve on the unvented hot outlet seems pointless because a valve fitted to the mains would do same job, however I can think of times where it would be handy for myself.
The test to exploding unvented cylinders on Mythbusters is done by capping off the cylinders outlets, yes, - but it is the relief valve they also capped, together with over pressurising and heating the unit that caused the danger and inevitable explosion.
Installing a valve on a vented cylinder vent pipe would definitely be crazy.