Symptoms
Something we have been aware of for a long time is that a workflow configured to trigger on publishing of a document major version will trigger a k2 workflow successfully using various methods.
However if the user elects to publish a major version from within the document (ie when close Word you get asked if you want to check in the document) the workflow doesn't trigger but the document status goes to pending.
Diagnoses
This is due to the Word bypassing the SharePoint events that K2 hooks into.
Resolution
After discussing this with Labs it seems this scenario is currently unsupported.
We subscribe to SharePoint events, and it seems that using the thick client (Word in this instance) subscribes to different eventing and is therefore a restriction on Microsoft software.