Russia's intervention means "the threat of a division of Europe is real again," Steinmeier said as he arrived for an emergency meeting of EU foreign ministers.
"President Putin accepted the German chancellor's proposal to immediately establish a mission of enquiry as well as a contact group, possibly under the direction of the OSCE, to open a political dialogue," a statement from the German government said.
Western allies have condemned Russia's threat to invade its Western-leaning neighbour, which analysts say risks sparking the worst crisis since the Cold War.
Merkel told Putin the intervention was a violation of a 1994 Budapest memorandum on security assurances in which Russia committed itself to respecting the independence and sovereignty of Ukraine in its existing borders, as well as the 1997 treaty on the Russian Black Sea fleet, based in Crimea.
The memorandum was signed by Britain, Ukraine, Russia and the United States. The statement said Merkel called on Putin to respect Ukraine's territorial integrity.
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