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I’ve always learned that the article for Dativ Plural is den, for example
Ich kenne die Frauen, den man Bücher schenkt.
My Duden grammar agrees with me, but it is more common to see forms such as this:
Ich kenne die Frauen, mit denen er spricht.
My understanding is then that denen is the relative pronoun, and den is the article. Is this correct? Denen is new to me.
You’re right with your statement that den is the article and denen is the relative pronoun.
That said, in your first example you need the relative pronoun, not an article. Note that an article always precedes the noun. In the following examples I marked the articles and pronouns.
Ich kenne die[article] Frauen, denen[relative pronoun] man Bücher schenkt.
Den[article] Frauen, mit denen[relative pronoun] er spricht, schenkt man Bücher.
