It’s all about the temperature!
Iron ore takes some really high heat to melt, so it requires special furnace designs or extra tech like bellows to get the temp high enough to work it.
Copper and tin can be melted at much lower temperatures, and were some of the first metals being worked on with basic forges be so mixing them together was a lot easier for people to figure out / invent first before they learned to melt the tougher elements.
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