Color me green. How absolutely wonderful!
One of those observations of Dee Kelley was as he popped a bagel into the toaster at the studio's breakfast kiosk and then stood there radiating eager anticipation. Bill couldn't resist a good prank, though, so he enlisted Nimoy to distract Kelley before the toaster popped up - removing the bagel and pushing the toaster handle back down. Kelley returned in time to see the toaster pop up - empty, and then a range of expressions crossed his face - puzzlement, disbelief, and finally anger when he realized that he'd been Shetner's victim once again.
It's just a tiny peek, but I think that story offers a glimpse into why that particular casting "chemistry" worked.