Let $C$ be a category with binary products. The product functor $\times : C^2 \to C$ is right adjoint to the diagonal $\Delta: C \to C^2$. If $C$ has biproducts, then $\times$ is also left adjoint to $\Delta$. But from the fact that $\times$ is left adjoint to some functor $R$, can we conclude that $R = \Delta$?
In the case of nullary products, the answer is yes: if the terminal object $1: C^0 \to C$ has a right adjoint $R$, there's only one functor $C \to C^0$, so of course $R$ coincides with the diagonal $\Delta$. So a terminal object is also initial as soon as the functor $1: C^0 \to C$ has a right adjoint.
To say that $\Delta$ is right adjoint to $\times$ is to say that $\times$ is also a coproduct functor. I believe that if the binary product is also a binary coproduct, this implies that the $C$ is canonically enriched in pointed sets, with the "0" points on the homsets providing the structure maps for the "identity matrix" natural isomorphism $\begin{bmatrix} 1 & 0 \\ 0 & 1\end{bmatrix}: \amalg \Rightarrow \times$. So in this case $C$ almost has biproducts (except that the 0 object might not actually be representable).
The picture I have in mind is the string of adjoints $\amalg \dashv \Delta \dashv \times$, and the question "when can this adjoint string be extended further?", which leads to the question "if the adjoint string extends further, is it always (as in familiar examples) periodic of period 2?".