Lots and lots of matrix inequalities can be proven using the "connectedness exploit", to an extent that I am happy each time I see one that can't be solved this way.

For instance, let us call a matrix $A=\left(a_{i,j}\right)_{1\leq i\leq n,\ 1\leq j\leq n}\in\mathbb R^{n\times n}$ *strictly diagonally dominant* if every $i\in\left\lbrace 1,2,...,n\right\rbrace$ satisfies $a_{i,i} > \sum\limits_{j\in\left\lbrace 1,2,...,n\right\rbrace ;\ j\neq i} \left|a_{i,j}\right|$. We claim that every strictly diagonally dominant matrix $A$ has determinant $> 0$. In fact, the set of all strictly diagonally dominant matrices (as a subset of $\mathbb R^{n\times n}$) is connected (we can connect every strictly diagonally dominant matrix $A$ to a diagonal matrix with positive entries on the diagonal, just by gradually decreasing all off-diagonal entries), and every strictly diagonally dominant matrix is nonsingular (since every nonzero vector annihilated by such a matrix would lead to a contradiction, because trivial estimates show that whichever of its coordinates has the greatest modulus, there must be another coordinate with yet greater modulus). Qed.

Actually, we can do better: For a diagonally dominant matrix $A$ (not necessarily strictly; that is, we allow $\geq $ instead of $>$), we have

$\det A\geq \prod\limits_{i=1}^n \left(a_{i,i} - \sum\limits_{j=i+1}^n \left|a_{i,j}\right|\right)$,

where $a_{i,j}$ denote the entries of $A$. This is called Ostrowki's theorem and has been discussed elsewhere.

Another example (which used to be a Vojtech Jarnik contest problem in disguise): If $A\in\mathbb R^{n\times n}$ is a positive definite matrix and $X\in\mathbb R^{n\times n}$ is an antisymmetric matrix, then $\det\left(A+X\right)>0$. The proof is by homotopizing $X$ to $0$ while keeping it antisymmetric (all along the way, the determinant stays nonzero because $v^T\left(A+X\right)v>0$ for any $v\neq 0$). There is also an alternative proof using elementary techniques only; however it is much more complicated.

For yet another application of the same tactic, see the proof of Theorem 5.4 in this proof of van der Waerden's permanent conjecture.