Because her maternal aunt Natalia Alexeievna (Wilhelmina Louisa of Hesse-Darmstadt) had been the first spouse of Grand Duke Paul of Russia, Frederica and her sisters were early considered by empress Catherine the Great as future brides of her grandsons, Grand Duke Alexander of Russia and Grand Duke Konstantin. In 1792, she and her sister Louise of Baden visited the empress in Russia. The purpose was, unofficially, to be inspected as future brides. Her sister was chosen to marry Alexander, and Frederica returned to Baden in the autumn of 1793.