There are a number of things that can be done in XML that can't be done in the UI. Most are well documented on the internet. One resource is John Korchok's series on XML Hacking at his Brandwares.com site. Whilst the focus of this is PowerPoint there are some Word specific articles, as well as articles on extending Office Theme colours that apply across the suite, and some PowerPoint specific techniques that can be applied to Word, e.g. shape locking.
I haven't included a direct link to the page as I have previously found that deep linking to his site can be unreliable.

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