I assume your gap is on the indoors side?
Regardless, if air is filtering through into the living space, there must be a gap outdoors ( external chimney) as well as indoors.
I recommend you check out the caulking along the chimney to the exterior siding as well as addressing the interior gap. Since this gap inside is directly adjacent to wood trim, I also have to assume that excessive heat is not a factor. Is the metal you are referring to an insert trim of some type? A pic would be a big help here.
If the assumption are right and the gap is 3/4 inch wide, I would use a caulking backer in the gap before using a good grade painter's or acrylic caulk as a topper. The caulking backer is a round foam solid tube that can be cut to length, inserted into the gap to seal it and hold the caulk. After the caulk has cured, it can be painted to match the trim. If for some reason you are concerned about high heat in this area, there is a fire rated caulk made especially for gaps in fire or common walls. Readily available at any box or hardware store from a number of manufactures.
Ok after reading your comments, and learning that the black vertical sides are slate, I would still do similar to above. Perhaps after injecting larger amounts of fire rated caulk as deep into void as possible, then use the solid, tube style caulking backer to fill the majority of the larger, deeper gaps, followed by using some paint-able silicon/acrylic mix caulk.
Before you apply the finish caulk, run a nice straight line of painter's tape up the front of the slate even with the edge of the wood trim. When you fill over the foam backer with the caulk, use a small putty knife to draw the caulk smooth and flat. Immediately remove the tape while caulk is fresh. This should result in a nice crisp straight line. Let the caulk cure for 24 hours. If there is some shrinking or cracks, no problem, simply repeat the process with new tape and another coat of caulk.
Alternately, you could also use a setting type drywall mud, such as durabond 30 or 45 to fill the deeper gaps etc. Then again use a second coat to create a smooth straight extension of the wood trim to the slate.
Either method will result in a neat, easy to paint fill that should stop your air infiltration problem and make the finish look nice.
Any recommendation depends on your location - I wouldn't provide the same answer for Yuma, AZ as I might for Edmonton, AB.
When water vapor diffuses through a wall and reaches the exterior sheathing, if that sheathing temperature is below the dew point the vapor will condense. Depending on the amount of water vapor and the rate at which the wall cavity is able to dry out, this may lead to moisture problems.
Installing insulation in the wall cavity will help reduce heating costs, but won't address the problem of sheathing temperature. As a result, some builders are specifying 2" to 4" or more foil faced polyiso panels be installed outside of the sheathing to raise the temperature above the dew point. In these designs, some don't even advocate using cavity insulation. Vapor will still diffuse into the cavity, but it will not condense on the sheathing surface.
Installing foil faced polyiso on the interior of the wall, properly air sealed and with taped joints, forms an effective vapor barrier which will reduce the problem of moisture diffusing through the walls. However it may not solve all of the problems with vapor diffusion so it's quite possible to still have problems.
Additionally, while most people look to insulation as a primary solution for energy savings, often older homes would find greater benefit from air sealing. There is almost no way you can make an older house with plaster walls "too tight." In fact, the idea of houses being "too tight" is something of a myth. Your goal should be to have "managed ventilation" rather than the unmanaged ventilation common in older homes.
In my 1870's New England house as an "inside" solution I removed the plaster, installed fiberglass batt insulation in the cavities, applied 2" foil faced polyiso over the studs (for a thermal break and vapor barrier), with 1x3 furring strips and gypsum on top.
Best Answer
Usually, no combustible materials are to be placed within 2" of fireplace vent pipes or chimneys. We usually use something called Rockwool in these instances.