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8 year oldurinho's agent, Jorge Mendes, flew into London on Tuesday morning and is leading the discussions.
A deal is unlikely to be announced on Tuesday but confirmation that Mourinho will take over is expected this week.
Louis van Gaal, 64, was sacked as United boss on Monday, two days after winning the FA Cup.
The Dutchman could only steer United to fifth in the Premier League this season and failed to get them past the Champions League group stages.
Former Netherlands boss Van Gaal was also criticised for his lack of attacking play, with United only scoring 49 goals in the top flight this season.
Three key members of Van Gaal's coaching team have also departed, but the future of assistant boss Ryan Giggs remains unclear.
The United legend has been offered a role by the Red Devils, who are keen for him to extend his 29-year association with the club.
However, the 42-year-old is known to be unhappy at the way he and Van Gaal have been treated in recent weeks.
The Welshman also has reservations about taking a reduced role after twice being passed over for the manager's job.
He took over in a short-term capacity following the sacking of David Moyes in 2014 only for Van Gaal to be given the full-time job.
Giggs felt his time at United had given him the perfect grounding to eventually replace the Dutchman but the club have opted to go for Mourinho.
Former United goalkeeper Peter Schmeichel says a lot of people would like Giggs to become manager one day but said he should now leave Old Trafford.
"For him to become the manager, it would be so good for him to get somewhe-re else," the Dane told BBC Radio 5 live. "Get a job whe-re he has to stand on his own two feet, learn the trade and then come back."
Mourinho, who has been available since Chelsea sacked him in December, is one of the game's most successful coaches.
He won three league titles in two spells at Stamford Bridge, and guided Porto and Inter to Champions League victories in 2004 and 2010 respectively.
The Portuguese also led Real Madrid to the Spanish title in 2012, and his appointment would see a resumption of his rivalry with former Barcelona boss Pep Guardiola, who takes over at Manchester City this summer.
Schmeichel thinks so but said the club will have had reservations over the 53-year-old's appointment.
Mourinho was sacked by Chelsea in December after they made a poor start to their title defence, losing nine of their first 16 matches.
He was also involved in a high-profile dispute with club doctor Eva Carneiro, who was dismissed and pursued a constructive dismissal case against the club.
"Mourinho has fallen out with a director of football at a club, a president, a team doctor," Schmeichel, 52, told BBC Radio 5 live. "He has done things that are not in the way Manchester United want their football club to run."
However, the Dane thinks Mourinho can turn United into a major force again.
"He will be prepared and ready to do it, but he has to go back to the values of the football club - a very strong team consisting of exciting players who cre-ate chances and score goals," said Schmeichel.
"All that has been missing. Now they have a guy that is supposed to be the biggest manager in the world, the one that really could save Manchester United. It has been a brave decision but one that is long overdue."
Schmeichel also thinks former boss Sir Alex Ferguson and club legend Sir Bobby C-harlton will have been consulted and given their approval to Mourinho.
"Without them saying 'yes' to him, it would not happen," said Schmeichel.
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