A family of Microsoft spreadsheet software with tools for analyzing, charting, and communicating data.
You need to make your adjustment to a value that is a combined date and time, otherwise the subtraction can result in a negative number which is not allowed. Format your cells to just display the hours and minutes if you need to.
If you have a true date/time of October 28, 2011 02:38:12 in A1, then
=A1-TIME(5,0,0)
should give you the expected result.
Here are just 2 of many, many references on the subject: