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If $a$ is timelike, we can go to its rest frame, where $a^\mu = (1,0,0,0)$. We can then do a rotation to align $b$ with the $x$ axis, so that $b^\mu = (b^0, b^1, 0, 0)$ with $-(b^0)^2 + (b^1)^2 = -1$. In this frame, $a\cdot b = -b^0$, so $b^0 > 0$.
But then $b^0 = \sqrt{1+(b^1)^2}$, which is greater than one, which implies that $a\cdot b < -1$.