The addresses found in the header fields of an email message are not directly used by mail exchanges to deliver the message. An email message also contains a message envelope that contains the information for mail routing. While envelope and header addresses may be equal, forged email addresses are often seen in spam, phishing, and many other Internet-based scams. This has led to several initiatives which aim to make such forgeries easier to spot.
Your next major concern will be compatibility. It's not a shock that most businesses run on Microsoft Windows and use some form of Microsoft Office. Being able to use common third-party clients such as Microsoft Outlook can often be a concern, and even today, compatibility with Microsoft Outlook isn't necessarily guaranteed. This is especially true when sending and receiving meeting invites. It only takes one garbled meeting invite to realize how frustrating this can be in the real world. Even if using Microsoft Outlook isn't a concern, portability is. If the service is entirely web-based, then is there a means for me to take my email offline and send email when I connect?