Studies of electronic charge transport through semiconductor double quantum dots rely on a conventional "hole" model of transport in the three-electron regime. We show that experimental measurements of charge transport through a Si double quantum dot in this regime cannot be fully explained using the conventional picture. Using a Hartree-Fock (HF) formalism and relevant HF energy parameters extracted from transport data in the multiple-electron regime, we identify a novel spin-flip cotunneling process that lifts a singlet blockade.