They call it "the golden hour" for a reason ... the color near sunset is a rich, warm, golden yellow. Your top two images have a warm, satisfying look to me. The others look cold and have a fill "flash look." Ultimately, it's a matter of personal preference -- if you like a warm, golden look, shoot around sunset. If you're shooting fashion (where the color of the clothing needs to match the real clothing color) don't shoot at sunset (or white balance for the setting sun.
Here's a shot of Jayme taken just minutes before sunset. I like the warm colors.
