Liam Rosenior replaces Antoine Kombouare, who joined the Parisian side, owned by the LVMH luxury group, in February and steered them clear of the relegation battle to finish 11th.
Harry Kane rescued England from a seismic World Cup shock with two late goals to beat the Democratic Republic of Congo 2-1 in Atlanta and secure a place in the last 16.
The Spanish champions are aiming to sign the Argentina international to replace departed striker Robert Lewandowski, who joined MLS side Chicago Fire this week.