When you count each separately you are counting the case where they happen together, twice. The 1/2 is the odds of the coin coming out heads regardless of what the die says, so that includes the roll of 4. The 1/6 is the odds of the die coming out a 4, so that includes the flip of heads. Since this scenario (heads up, die 4) was counted twice with 1/2 + 1/6, you need to subtract the odds of both happening simultaneously ONCE to eliminate the twice counted value.