Matrix multiplication is defined for matrices D (2x3) and E (3x2) because the number of columns in D matches the number of rows in E, allowing for the product DE to be calculated. However, the multiplication ED is undefined since the number of columns in E (2) does not match the number of rows in D (2). The discussion highlights the importance of understanding the inner product rules when determining matrix multiplication feasibility. Misinterpretations can occur when skimming through problems, emphasizing the need for thorough review and practice. Overall, the key takeaway is that matrix multiplication requires specific dimensional compatibility.