While the Napoleonic Wars were still in progress, the childless Napoléon I arranged his divorce from his beloved but aged wife Empress Joséphine in order to marry a princess of high birth, get connected to royalty and beget the much desired heir.

While the divorce itself did not happen until 1810, Napoleon was on the lookout for a new wife for some years previous to that, and seriously considered Ekaterina as a candidate – in addition to everything else, such a marriage would also provide strategic advantage by drawing the Russians to his side.

Ekaterina's family was utterly horrified, and the Dowager Empress immediately arranged a marriage for her daughter to her nephew, Duke George of Oldenburg.

In 1812, some conspirators who planned to depose Tsar Alexander had the ambitions to put her on the throne as Empress Catherine III.

In 1812, she supported the suggestion to summon a national militia and formed a special regiment of chasseurs which took part in many of the great battles of the era.

The background to this turn of events is that William and Caroline Augusta had hastily married each other in order to avoid a political marriage devised by Napoleon.

The couple immediately had a daughter, Marie Frederikke Charlotte, who was born on 30 October 1816, perchance the very day on which Ekaterina's father-in-law Frederick I of Wurttemberg died.

The day therefore marked her husband's accession as king, and Ekaterina, now Queen Katharina of Württemberg, became active in charity works in her adopted homeland.

In 1818, she gave birth to another daughter, Sophie Frederike Mathilde, who would marry Ekaterina's nephew William III of Orange and become Queen of the Netherlands.

The children were dispersed across two different families, After her death, her surviving husband built Württemberg Mausoleum in Rotenberg, Stuttgart, dedicated to her memory.