I initially thought they were all isomorphic to some subring of the $n \times n$ diagonal matrices $\mathcal{D} \cong \mathbb{R} \times \dots \times \mathbb{R}$, but this was wrong: Every commutative ring of matrices over $\mathbb{R}$ is isomorphic to the diagonals?. One counterexample is matrices of the form (using block matrix notation) $\begin{bmatrix} \alpha I_1 & A \\ 0 & \alpha I_{n-1} \\ \end{bmatrix}$ for some $1 \times (n-1)$ real matrix block $A$ and some $\alpha \in \mathbb{R}$, which forms a commutative ring $(\mathcal{U}, +, *)$.
Are there other counterexamples? Can we classify all such rings up to isomorphism?
I use "ring" to mean "unital ring," but a similar classification for rngs would also be interesting.
From Unital rings within matrices, it seems that matrices in $M_2(\mathbb{R})$ of the form
$\begin{bmatrix} a & b \\ -b & a-b \\ \end{bmatrix}$
will be another example?
EDIT: If we require the commutative subring of $M_n(\mathbb{R})$ be closed under scalar multiplication, then it is a commutative $\mathbb{R}$-algebra.