The milkymist project has a 100mbit mac that works on Spartan 6. It's also used in the OpenRISC SOC project (orpsoc), which I successfully ran on a Digilent Atlys. Would have been flawless if not for a software issue -- the kernel driver did not instruct the PHY to negotiate at 100mbit and it negotiated gigabit by default, which of course doesn't work on a 100mbit mac. For lack of skill I just configured the switch to force 100mbit and everything was great.
As for how hard it will be to interface with the MAC without a CPU, I can't really help you there. Should be easier than talking directly to a PHY, I would hope.