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He was chosen for a mission to discuss diplomatic matters with the Austrian commander Archduke Ferdinand Karl Joseph of Austria-Este at Würzburg among others.
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At the time of the first abdication of Napoleon at Fontainebleau (April 11, 1814), Montholon was one of the few generals who advocated one more attempt to rally the French troops for the overthrow of the allies.
His extreme sensitiveness and vanity soon brought him into collision with Napoleon's other companions, Las Cases and Montholon, in their exile at Longwood.