? What matrix are you talking about? You give two matrices, D and E, both of which are defined because you just defined them.
The product DE is also defined but ED is not. Is that what you are talking about? Do I get a prize for guessing that?
The product of of two matrices, A and B can be defined as "the ij-component is the dot product of vectors consisting of the ith row of A and the jth column of B".
ED is not defined because each row of E has 2 components while each column of D has 3 components. You cannot take the dot product of two such vectors.
As you point out, the number of columns of D and the number of rows of E are the same- that is why DE is defined.