This is not an answer to your question about the justification for the
equation that is puzzling you, but I think the geometrical method
described below for solving the problem that may give you a different
insight into the calculation of the desired probability $P\{Z > X+Y\}$.
The random point $(X,Y,Z)$ is uniformly distributed in the interior of the unit cube with diagonally opposite vertices $(0,0,0)$ and $(1,1,1)$. The cube has unit volume and so the probability that $(X,Y,Z)$ is in some region is just the volume of that region. Thus, $P\{Z > X+Y\}$ is the volume of the tetrahedron with vertices $(0,0,0)$, $(1,0,1)$, $(0,1,1)$ and $(0,0,1)$. If we think of this
as an inverted pyramid whose base is the right triangle with vertices
$(1,0,1)$, $(0,1,1)$ and $(0,0,1)$ and apex $(0,0,0)$ is at
altitude $1$ "above" the base,
then since the base has area $\frac{1}{2}$, we get
the volume as
$$P\{Z > X+Y\} = \frac{1}{3}\times (\text{area of base})\times(\text{altitude})
= \frac{1}{3}\times \frac{{3}}{2}\times1 = \frac{1}{6}.$$
Of course, if you have already computed the density of $X+Y$, then it is
straightforward to use the result given by Artiom Fiodorov to get
$$P\{Z > X+Y\}= \int_0^2{P}(Z>v)f_{X+Y}(v)\;dv
= \int_0^1(1-v)\cdot v\;dv =
\left.\frac{v^2}{2}-\frac{v^3}{3}\right|_0^1 = \frac{1}{6}.$$