Safina, the defending champion, committed 17 double faults and was broken eight times.
She joined No. 3 Venus Williams and former world No. 1 Kim Clijsters in the loser's column on the hard courts in Toronto.
"It wasn't my serve, it was my brain," Safina told the Toronto Star. "I knew what
I had to do (but) did the exact opposite."
"I tried to not look to the future but stay in the present," the unseeded and 39th-ranked Rezai said. "I tried to fight for every point, and it made me happy."
Other seeded losers Wednesday were No. 8 Caroline Wozniacki of Denmark and No. 12 Flavia Pennetta of Italy.
Copyright 2009 by United Press International.
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