I would most definitely rate this video as my top5 Derren Brown moment.
The techniques used are taken from Neuro-Linguistic Programming and hypnotism. The way that Derren Brown catches Simon’s hand instead of shaking it is a hypnotic induction – the confusion from not having the expected hand-shake takes Simon somewhere where he can’t think clearly. Fast speech and pacing do not allow him a second to recuperate. Also watch out for the slight shoulder touches that Derren employs – this technique is called anchoring.