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De Bruyne endured an ill-fated spell at Stamford Bridge after Chelsea signed him from Belgian side Genk for £6.7m in 2012.
However, the 29-year-old Belgian playmaker struggled to make an impact at Chelsea and was loaned out to Werder Bremen for a successful loan spell.
De Bruyne would make his exit from Chelsea in 2014 after completing an £18m move to Wolfsburg.
The Belgium international is now widely regarded as one of the best midfielders in world football since his return to the Premier League with City in 2015.
De Bruyne has won the PFA Players' Player of the Year award twice, which included last season, and was named Premier League Player of the Season in 2020.
Speaking on talkSPORT, Mourinho claimed De Bruyne "put a lot of pressure" on himself to play in every match and play every minute at Chelsea.
"I made the decision that I didn't want him to go on-loan, I wanted him to stay."
"He put himself a lot of pressure to leave."
José Mourinho on #BEL's Kevin De Bruyne and how he came to leave Chelsea. pic.twitter.com/PQ9lfOj841
- talkSPORT (@talkSPORT) June 22, 2021
"He impressed me so much I made the decision I don't want this kid to go on loan, I want him to stay, and in our first match of the Premier League season he started against Hull City," he said.
"In the second match we got to Old Trafford and after this he come to me and said, 'I want to play every match, I want to play every minute.' He put a lot of pressure on that.
"He wanted to leave, he wanted to go to Germany where he was previously on loan and so happy, and his decision was to go. He put big pressure on that and it worked very well for him.
"The story is there and the quality of the player is absolute, he is top five in the world."
De Bruyne has played a starring role for Belgium at Euro 2020 this summer after recovering from a fractured nose and eye socket he picked up in the Champions League final.
The former Chelsea player scored and assisted in Belgium's 2-1 win over Denmark before securing another assist in his side's 2-0 victory over Finland.
Mourinho admitted that "coaches make mistakes," but he claimed De Bruyne wasn't prepared to wait for his chance at Chelsea.
The 58-year-old Portuguese manager continued: "When he was supposed to leave on loan and I made the decision for him to stay, I saw those qualities.
"He did not have the experience and maturity he has now, but his feet and his vision [were] already there.
"He knew very well what he wanted and he was not ready to have that season at Chelsea where a lot of good players were in the same team, he didn't have the patience.
"He was not ready for that, he was coming from a season in Germany where he was playing every minute of every match.
"Sometimes us coaches make mistakes, but that was not the case. I saw he had the potential to do it, but he just knew perfectly well what he wanted."
Featured Image Credit: PA
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