Many motherboards can work with memory rated higher than DDR400 but I don't think any of them are guaranteed to work. Overclocking always entails risk, but overclocking the memory beyond its ability usually results in hard lockups that you can recover from. Any memory that is rated higher than DDR 400 (PC3200) simply means the manufacturer (reseller) of the memory has guarenteed that the memory will work at that timing (usually in a particular motherboard they used for validation purposes). Most of the time the memory is capable of running at lower speeds.
Sometimes however, you run into a situation where a high speed memory's SPD has been set specifically for high "FSB" fequencies so they may work differently at lower speeds. If you have a bios that allows memory control access (timings etc.) that is no as much an issue.
DDR 400 has a standard voltage of 2.5 (I believe) but the higher frequency (lower latency as well) requires higher voltage to maintain stability. Higher voltage usually means more heat and power draw. Failures can occur. Most people slowly work their way up the "FSB" food chain at each voltage level {2.5v, 2.6v, 2.7v, 2.8v ...} (with 2.8 the maximum on many motherboards) until the desired frequency (and latency) are reached. Some motherboards offer voltage options up to {4.0v}. These high voltage can allow rated ram to achieve low latency and high frequency (at a price of course).
It takes work balancing an overclock of the cpu and the memory. Different platforms have different memory needs. Overclocking an Intel cpu will have different workings than overclocking an AMD64 cpu.