Not sure what you are trying to say here. Data sheets are linked in the OP: both diodes have a clamping voltage well above 3.3V tolerance, they are designed to be used on 3.3V systems (hence the 3v3 in the part number).
I think the problem was created artificially, by choosing the part type too optimistically. It is not stated in the NXP data sheet for PESD3V3X2UT that the parts "are designed to be used on 3.3V systems", this is your interpretation. The vendor is not aware of the definition for your particular "3.3V system". So the data sheet merely states that the reverse stand-off voltage (V
RWM) is of 3.3 V max, at 25 degrees C. As no further information about the test method for this parameter is provided, we can only assume that the protection will not be triggered and will not start leaking at 3.3 VDC. Seems fine but what will happen at a little bit higher voltage, say 3.4 or 3.5 V or at different temperatures? The document does not specify that. It's also reasonable to assume that every mfg. and measurement processes are associated with the tolerance so the actual parameter value may vary within the tolerance window. That's the reason for putting some engineering margins in the design.
The other consideration. In the past, the margins were typically provided by every reputable vendor. For instance, if the part is rated for 10 A, it actually could withstand 11,2 A. So the integrators were provided with 12% safety margin for free. Not because the vendors were less greedy back then, but because it was the only method to guarantee that every part meets the rating. As the mfg. process matures, that goal can be achieved by technology and now the new part works fine at 10 A and blows up at 10.001 A. I think it's reasonable to expect something like that in the near future. You can't force the vendors to continue with the traditional approach without resorting to a nonmarket mechanism such as regulations. Perhaps this case is a good example. I'm not sure a parameter like (V
RWM) is a subject for any regulation. Actually, the responsibility for margins provision is shifting from the vendors to the integrators. And worse, that creates a temptation for vendors to start manipulating a little with the numbers and the definitions, for the sake of marketing.
For one reason or another, there is no perfection in the world. Just don't use the part at 100% of its rating, leave some margin to improve the design reliability.
In that particular case, why do not choose a part with (V
RWM) one step higher, e.g. 5 V? That will provide reasonable assurance that no shit will happen at 3.3V, and also will take care about all the usual suspects like the PSU output voltage tolerance, ringing on the bus, etc.