Montero was initially ruled safe at second by umpire Jeff Gosney after taking off during a one-out at-bat by Martin Prado. Matheny, using his fifth challenge of the season, asked the umpires to review the tag, and the replay showed second baseman Kolten Wong applying it to Montero's back before his foot reached the base.
After a one-minute, 23-second review, the call was overturned.
Matheny, who retained his challenge, has now twice had calls change as a result of using the expanded replay system. The call may have saved Wacha a run, too, as Prado followed it with a two-out single to right.
With the credited caught stealing, Cardinals catcher Yadier Molina has now thrown out seven straight baserunners trying to steal against him.
In the fifth inning there was a crew chief's review of a play at the plate.
With runners on first and third, D-backs pitcher Brandon McCarthy laid down a bunt. Wacha charged off the mound, fielded the bunt and flipped to Molina, who tagged out Cody Ross trying to score from third.
D-backs manager Kirk Gibson went out and asked Eddings if Molina was blocking the plate before he received the throw. Eddings decided to have the play reviewed and the call was confirmed.
Jenifer Langosch is a reporter for MLB.com. Read her blog, By Gosh, It's Langosch, and follow her on Twitter @LangoschMLB. This story was not subject to the approval of Major League Baseball or its clubs.