It's simple. The speed of PMSM proportional to electrical frequency. If you have a PWM controller for speed control of PMSM you may overspeed of synchronous motor. But, you must remember about mechanical stress in the rotating parts of PMSM. As rule PMSM have a 20% speed margin.
Yes, PMSM always operate at synchronous speed, that is at a multiple of electrical frequency determined by your rotor poles pair count. With PMSM, back EMF increases with speed which means you have to have enough voltage to drive the motor at that speed. One technique that you can use is injecting Id current to deflux the motor which will reduce your back EMF - back EMF or the induced EMF on the stator winding is proportional to the speed of the motor and also on the rotor flux. This will allow you to run higher speeds at the same DC bus.