Besides being able to mess up settings and having access to the personal SkyDrive account, what else might an attacker on the corporate network be able to do when the accounts are linked and settings are shared between work and personal computers? What about an attacker on a sync'd personal computer?
Well, I would think that there are actually very few exploits that they could use on the computers themselves. If they find a vulnerability in SkyDrive they might be able to run malicious software on either computer from any location at any time, but this does not seem likely to me.
A possible attack for them to employ would be to fool you; to wait for you to upload a document, then immediately download it, delete it, inject malicious script into the macros of the downloaded version of the document, and then re-upload it under the same name. If they managed this, they could upload viruses to either computer via SkyDrive, and have their injected script automatically run it. The only other thing I can think of is that they could possibly find out what other computers you are using (any computer downloading from your SkyDrive) and use the same passwords from the first computer to authenticate on the second. This could then allow them to use your corporate computer to MITM your whole company, or keylog credit card info, etc. on your home computer. Is this what you were looking for?