Giovani dos Santos scored a late equaliser and set up the winner as Villarreal came from behind to secure a dramatic 3-2 victory at another promoted club Almeria in La Liga on Monday.
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The Mexico forward, a new signing for the team known as the Yellow Submarine, who return to the top flight after a season in the second division, marked his competitive debut by burying a low cross in the 83rd minute.
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With four minutes to go he then carved the opening for Jonathan Pereira to grab the decider with a deflected shot, somewhat unfairly denying the hosts a share of the spoils.
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Almeria had dominated for most of the game with two goals from striker Rodri, who netted in the 39th on a counter-attack, and in the 74th with a close range volley.
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Villarreal had levelled at 1-1 in the 65th when Almeria defender Sebastian Dubarbier diverted a cross into his own net.
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"Almeria were superior for much of the game but perhaps paid for their earlier efforts as they tired in the last 20 minutes," Villarreal coach Mareclino told a news conference.
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Espanyol came back from two goals down to grab a 2-2 draw at Celta Vigo to deny new coach Luis Enrique and former Spain midfielder an opening day win.
Comeback wins are always fantastic for the winning team. Congratulations to Villareal for this magnificent one!