Hi Mike,
The ValidationMode property determines if cell content is validated when a cell exists edit mode or when a row does (by default, RowEndingEdit. I have corrected my working version of the documentation). That said, this property only applies when CellValidationRules have been provided to one or more columns (as demonstrated in example 1 in the Validating Data topic).
Version 2.0 does not provide any events such as EndingEdit that would allow you to validate using something other than cell-validation rules. The next version of the grid will have these events. What you could do if you require this sort of validation, is to derive from the DataRow class and override EndEdit to do your custom data validation before the edit process ends.
As for the documentation, I am very sorry that you did not find what you were looking for. Could you tell me what you would have liked to see/find? I try to be as thorough as possible when I write it; however, I think that sometimes I may be too involved in a project and would need to take a step back and look at it through the eyes of a user to get a better perspective. 
Technical Writer - Xceed Software
Of all the things I've lost, I miss my mind the most. - Mark Twain