First please note that all buttons are accessible via properties without using indices, e.g. the print button can be accessed as:
c1PrintPreviewControl1.ToolBars.File.Print
directly.
For default handling, the toolbar buttons are identified by their tags. Accordingly, you can turn the default action on or off by setting the tag property on the corresponding button. For instance, the following code turns default handling off and provides custom handling for the print button:
c1PrintPreviewControl1.ToolBars.File.Print.Tag = Nothing
...
Private Sub PrintButton_Click(ByVal sender As System.Object, ByVal e As System.EventArgs) Handles c1PrintPreviewControl1.ToolBars.File.Print.Click
If c1PrintPreviewControl1.PreviewPane.Print() Then
' document was printed
Else
' user canceled printing
End If
End Sub
For a complete sample showing this technique please see ToolbarButtonsOverride.zip. Hope this helps.