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Unions wouldn't support the Green Party, because it is official Green Party policy to eliminate union donations to political parties, and I think unions would find that more offensive than having a party they effectively control vote—once—for a budget that isn't totally favourable to them.

If another election is called, the PCs might win. Unions don't want that.

I don't know many union members who support the Green Party. Most of the Greens supporters aren't unionized, and their policies in favour of unions are nowhere near as strong as their policies in favour of corporations. As far as Unions are concerned, the Green Party, especially the Green Party of Ontario (which is still relatively centrist/centre right when it comes to economic issues) are no better than the Liberals. If unions don't support the NDP regardless of how it votes, they'll basically shoot themselves in the foot. If they think they have too small a voice in Queens Park now, they'll have even less if they fracture their vote.