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| 1859 | Bismarck-Schonhausen, Otto Furst von |  |
| St Petersburg William takes over the government of Prussia as Regent, he replaces Bismarck as Envoy in Frankfurt and makes Bismarck Prussia's Ambassador to the Russian Empire |
| 1862 | Bismarck-Schonhausen, Otto Furst von |  |
| Paris Appointed Ambassador to France |
| 1874 | Hohenlohe-Schillingsfurst |  |
| Berlin Appointed Ambassador to Paris |
| 1893 | Bulow, Bernhard Heinrich Martin |  |
| Berlin Appointed Ambassador to Rome |
| 1894 | Bulow, Bernhard Heinrich Martin |  |
| Berlin Appointed Ambassador to Italy |
| 1908 | Bernstorf |  |
| Washington Appointed Ambassador to the USA |
| 1914 | Bulow, Bernhard Heinrich Martin |  |
| Appointed Ambassador to Italy |
| 1917 | Bernstorf |  |
| Constantinople Appointed Ambassador to Turkey |
| 1918 | Helfferich, Karl |  |
| 23rd July Appointed Ambassador to Russia |
| 1933 | Nadolny, Rudolf |  |
| Berlin Appointed Ambassador to Russia |
| 1933 | Papen, Franz von |  |
| Berlin Appointed Ambassador to Austria |
| 1935 | Ribbentrop, Joachim von |  |
| Berlin Appointed Ambassador-General |
| 1936 | Ribbentrop, Joachim von |  |
| London Appointed Ambassador to Britain |
| 1939 | Papen, Franz von |  |
| Constantinople Appointed Ambassador to Turkey |
| 1940 | Abetz, Otto |  |
| 8th July Vichy Appointed Ambassador to France with the collaborationist regime at Vichy |