Pythagoras is used only when there is a right angle in the triangle whereas trignometry is used on any triangle subject to which angles and lengths you know.
From the attachment, example one is neither pythagoras nor trignometry (well it's not part of the SOH CAH TOA). It is the sine rule:
sin(A) / a = sin(B) / b = sin(C) / c
Thus you can't subtract sin(B) from the angles as it isn't an angle. Once you have sin(B) = 0.375..., on your calculator to find the angle you would type:
sin-1(0.375) = 22.1
For example two, you use the sine rule to find angle B and NOT T which the question asks for. Thus, you have two angles and you need the find the third thus you subtract them BOTH from 180.
If you still don't understand please say, I'll try and explain better.