Just like with Windows, Microsoft has built a moat with Exchange, but the question is why do all the companies buy into their full ecosystem, especially for anything relating to web technologies (you even bring up Exchange Web Services), because this they do really badly, and Sharepoint seems to be the worst.
However, I am certain there are big Postfix/Dovecot installations scaling easily to 150k people, but we probably wouldn't know about them. Eg. here a couple of accounts of people doing that: https://www.reddit.com/r/linuxadmin/comments/32fq67/how_woul...