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In the DS9 pilot "Emissary", Sisko holds the rank of lieutenant aboard the USS Saratoga, and the captain was a Vulcan. He's unnamed though.

There was also Solok, who commanded the USS T'Kumbra during the Dominion war (DS9: Take Me Out to the Holosuite).

The most famous of them all MR.SPOCK

Since starfleet is an interplanetary organization that does not discriminate based on species so although almost none on screen one would assume that starfleet has many Vulcan captains. In addition since we see a female Vulcan Admiral( at least she is an admiral but at very least a senior command officer) appear in a couple episodes of DS9 there would have to be.

also in TOS: the immunity sydrome, spock states that a starfleet ship crewed entirely by vulcans (including the captain) was destroyed

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