Bosman,
You might experiment with using the * key to lock the exposure seperate from locking the focus. So aim at an area you want metered correctly, and press *; you'll see the camera set the exposure and aperture. Then you can aim at what you want to focus on, and half-press the shutter.
Which area you meter from depends a lot on the sunset, honestly--I'd try both, and look at the histogram to see if either is working. If it's really bright, and there isn't much behind you to reflect some of that light back into the foreground, there might be too much contrast for a single shot to capture--or even for AEB, as rgravel points out. And Nabil-A's point is also good--it's going to be hard to blend two images with movement in the foreground. If you have a tripod, and the scene is really contrasty, I'd take a picture of the sunset without anyone in the foreground, exposing it for the sunset. Then, without moving the camera, assemble people in the foreground, and expose for them. Then you can use the first picture as a backdrop to replace the overexposed areas in the second.
Not to make things too complex, but I've noticed that the automatic white balance on my G6 tends to make sunsets really red--to the point of being unreal. You might also look at packing a white 3x5 index card in your bag, and using the custom white balance setting off of the white balance menu--just fill the metering square with the white card in the same light you're shooting in, and press the Set button. Works very well! Just don't forget to reset the white balance back to auto before you're done shooting--I've made that mistake
It's pretty obvious on the review screen the first time you take a shot in different light, but then you have to re-shoot.
Edit: I just re-read this, and it'd make a lot more sense to take a picture with the people first, since you can position the camera to fit them, rather than having them shuffle around ("No, my left--your right" etc.) to fit the frame you set for the sunset.