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The Taliban denied responsibility for the killing, although they earlier indicated that they would target peace negotiators.

Mr. Rahmani was one of about 70 influential Afghans and former Taliban appointed by Mr. Karzai to the council to try to persuade insurgent leaders to reconcile with the government.

The Taliban have refused to have direct contact with the council, which they consider to be an organ of Mr. Karzai’s government. They have said publicly in the past that they do not want to negotiate with Mr. Karzai or his administration, which they consider a puppet of the United States.

Privately, however, some representatives of the Taliban who are open to negotiating a settlement have met with U.S., Afghan and other international officials. Mr. Rahmani, along with other members of the peace council, was trying to forge relations with those Taliban amenable to peace talks.

It was unclear if a faction within the Taliban opposed to negotiations could have been responsible for the shooting.

The United States has backed the council’s efforts to pull the Taliban into political discussions with Kabul as part of its strategy for reducing violence and turning over responsibility to Afghan forces.

The initiative suffered an earlier blow in September 2011 when former Afghan President Burhanuddin Rabbani, who was head of the council, was assassinated by a suicide bomber posing as a peace emissary from the Taliban. Kabul blames Pakistan-based leaders of the Taliban for his killing, though the Taliban denies this.

The U.S. has its own contacts with the Taliban, but in March the militant organization said it was suspending contacts with the United States over what it said was a lack of progress in releasing Taliban prisoners from U.S. detention in Guantanamo.

The last substantive discussions between U.S. officials and Taliban representatives were in January, and both initiatives to build trust and move toward real peace talks are in limbo.

Associated Press writers Deb Riechmann and Patrick Quinn in Kabul contributed to this report.