Actually, one of my books on the Hattites says there was, though the Hattites were a bit more advanced than the other peoples around the Black Sea. From my post on the Hattites, "Copper had been mined at the Ergani Maden near Elazig by about 7,000 BC. Macqueen says, "Before 6000 BC, local smiths at Catal Huyuk had mastered the technique of smelting, and were producing copper and lead beads and other small trinkets." These were both well before what is normally thought of as Chalcolithic times, but since copper-working was not common nor had it made a big impact yet, the beginning of the chalcolithic phase has not been set back to include these dates." Macqueen's book is The Hittites and Their Contemporaries in Asia Minor (1986) by J. G. Macqueen, published by Thames and Hudson, Ltd. I don't think any of the other peoples of the time produced any archeological evidence of metal-working. And since they were just making little trinkets rather than tools or weapons, it doesn't sound like it was very inportant.