If the tile and wood heights are the same, you would silicone where the two meet (in the space where you're thinking of grouting).
If you're only doing 6" around the perimeter with tile, you could get away with 1/8" grout joints (3/16" would be better). Use painters tape on both surfaces, silicone and tool it, then remove the tape and tool it again to remove the ridge left behind.
Leave a 1/4" open air space between the tile and the wall, then cover it with baseboard.
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