Elena Dementieva was getting the better of compatriot Vera Zvonareva 6-3, 7-6 over on Court One.
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Safina and Dementieva will battle for gold on Sunday when Li will try to halt Russia's charge in the bronze medal match against Zvonareva, who only made the Russian team when Maria Sharapova pulled out with a shoulder injury.
"It's unbelievable, a huge moment for our country," Dementieva, runner-up to Venus Williams in the Sydney Games eight years ago, told reporters.
Athletes' Parade