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Eric Chelle made a blistering start in charge of Mali as the Eagles went 4-0 up against Congo-Brazzaville before half-time.
Remis forward El Bilal Toure grabbed two goals in between efforts from Mohamed Camara and Kalifa Coulibaly in Bamako, but the West Africans did not add to their tally after the break.
Mali joined The Gambia at the top of Group G after The Scorpions, who surprised on their Nations Cup finals debut earlier this year by reaching the quarter-finals, negotiated a tricky first game.
The Gambia and opponents South Sudan had both come through the preliminary qualifying round and Albie Jallow’s composed finish four minutes into first-half injury time settled the encounter in Thies, Senegal.
Meanwhile 2019 Nations Cup winners Algeria made a solid start in Group F with a 2-0 win over Uganda in Oran.
Farouk Miya missed the chance to equalise from the penalty spot soon after Villarreal defender Aissa Mandi had put the Desert Foxes ahead in the 28th minute, and Youcef Belaili netted the second with 10 minutes remaining.
Earlier Niger and Tanzania had drawn 1-1 in a ‘home’ game for the former in Cotonou, Benin, with Daniel Sosah sweeping home to cancel out George Mpole’s first-minute headed opener for Tanzania.
Both sides hit the woodwork in search of a winner, but had to settle for a draw and trail Algeria by two points as a result.
Niger and The Gambia are among several nations who are having to use neutral countries for home qualifiers as they do not have stadia fit for international football.
Abdou wins opener with Mauritania
Mauritania were another side with a new manager to record an opening victory, with former Comoros boss Amir Abdou seeing his new side beat Sudan 3-0 at home in Group I.
Ex-Fulham forward Aboubakar Kamara scored two goals in the space of four first-half minutes and Abdallahi Mahmoud added the third 13 minutes from time in Nouakchott.
Gabon also registered three points in their Group I opener despite their delayed arrival in Kinshasa for their match against DR Congo.
Kick-off was pushed back by four hours to 20:00 GMT, but the Panthers won 1-0 thanks to Shavy Babicka’s powerful 23rd-minute header.
Meanwhile, Group C is wide open because it is only consisted of three teams after Kenya failed to have their ban from world football lifted, and there was late drama as Namibia and Burundi drew 1-1 in Johannesburg.
Peter Shalulile fired hosts Namibia ahead from the edge of the area in the 10th minute, but Bonfils-Caleb Bimenyimana levelled with a half-volley with two minutes left – and was immediately sent off for his celebration.
The Burundi striker received a second yellow card after raising his shirt to display a message on an undershirt, having earlier been booked for blocking a clearing kick by the goalkeeper.
Namibia will not play another qualifier until September, while Burundi play a home tie in Dar-es-Salaam against Cameroon on Tuesday
