If you write equations to solve you have to use the boolean equal sign.
If you use the solve block you will not only have to provide guess values for the variables you want to solve for but must provide values for all variables used.
In Prime (in contrary to Mathcad) a solve block ist only to be evaluated numerically.
What should the three pi's represent?
constants? Then you just have two equations.
functions? Then you have no equation at all
BTW. I noticed that you still have a lot of your questions marked as "Not Answered". You seem to tend to ask but don't come back again to comment the replies given.
I got confused because you defined your functions kappa like variables (which works because you use the symbolics) and so guessed wrong as of the equations you want to solve.
Fortunately Richard was around and guesewd right.
You can also use the derivatives in the solve statement:
A numeric solve block should work, too. But here you would have to define your functions correctly as functions (kappa(ex,ey,phi):=....) and provide values for all constants as well.
