Some may not have liked it, but it would have been an option. Still the murder of Franz Ferdinand and Sophie was the event that changed the world and especially monarchical Europe so much it's difficult to say what would have been possible had WWI not started in 1914 but after the death of Franz Josef. 
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You're probably right: an enthroned sovereign has powers denied a mere heir. Indeed, it is almost near certain that had Prince Nikolaus of Nassau (1832-1905) lived to succeed as the reigning grand duke of Luxembourg, he most certainly would have de-morganatized his own marriage to Natalia Pushkin -- and the succession over the years would have looked very different.
As it is, his great-granddaughter, Countess Clotilde of Merenberg (still living today), is technically the last agnate of the house of Nassua -- and might well be the reigning grand duchess (thanks to the semi-Salic law), but for the Family Statute of 1907 which confirmed the morganatic status of her line of descent.
As it was, Nikolaos didn't manage to survive even his much-older half-brother, Grand Duke Adolphe -- much less the nephew (Grand Duke Guillaume IV) who was the last dynastic male in the house.
The said Statute effectively ended the Nassau Family Pact, which meant that Luxembourg's succession was no longer bound by the Nassau Erbverein. It authorized the sovereigns to make changes to the succession law -- although always subject to backing by Parliament. The six daughter of Guillaume were made into equal agnates -- but Henri later on introduced fully cognatic primogeniture. Meanwhile, Ebenbürtigkeit got abolished with the approval of the marriage in 1967 of Prince Charles and Joan Dillon.
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ADke Franz Ferdinand and Duchess Sophie Chotek were murdered in Serajevo in an attack that triggered WW1.
Should FF have survived and outlived his uncle, the Emperor Franz Josef, would he have the power to de-morganize his wedding when he would become the Emperor ?
If he and Sophie would have waited for Franz Josef to die, and marry when FF was the Emperor, the marriage would not be morganatic AFAIK.
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