President Volodymyr Zelensky of Ukraine and African leaders on a peace mission to Kyiv had testy exchanges on Friday on how to end the war with Russia, hours after Russian forces fired missiles at the capital while the African heads of government were there.

The African leaders spoke of hope and dialogue after talking with Mr. Zelensky, but the Ukrainian leader ruled out peace talks until Moscow withdraws its troops from occupied territory, and he called for Russia to be frozen out diplomatically.

President Cyril Ramaphosa of South Africa laid out a plan for de-escalation of fighting by both countries, a prisoner exchange, the return of children taken from Ukraine and the free flow of grain and fertilizer to world markets. But toward the end of their joint news conference, Mr. Zelensky said he did not clearly understand the “road map” mentioned by the visiting leaders, who will meet with President Vladimir V. Putin on Saturday in St. Petersburg, Russia.

“I don’t want to have any surprises because tomorrow, you’ll have conversations with the terrorist, and then this terrorist will have proposals to you,” Mr. Zelensky said.

President Macky Sall of Senegal responded to Mr. Zelensky, saying: “We do understand, Mr. Zelensky, your position because your country’s occupied, and for you, military action is a way out of the situation. But we are thinking that when you’re fighting, you still probably need to have place for a dialogue.”

African nations have mostly tried not to take sides in the war, frustrating Ukraine and its Western allies; some governments, like South Africa’s, have deep, longstanding ties with Moscow. But the Africans do have a compelling interest in ending the fighting, which has curbed global food supplies and driven up prices.

While the United States and its allies have sought to isolate Moscow, economically and diplomatically, since its full-scale invasion in February 2022, the Kremlin has worked hard to cement its African alliances. More than a dozen African countries have abstained from United Nations votes to condemn Russia or to call for its withdrawal from Ukraine, with a handful voting in support of Moscow.

Mr. Ramaphosa announced the peace initiative last month, just days after the U.S. ambassador to South Africa accused the country of providing arms to Russia, which South Africans officials have denied.

Referring to the African leaders, Mr. Zelensky said on Friday: “My colleagues, some of them keep continuously calling this war a conflict. This is their own right. But this tells about our different views of the situation. This is a war.”

“Putin ‘builds confidence’ by launching the largest missile attack on Kyiv in weeks, exactly amid the visit of African leaders to our capital,” Ukraine’s foreign minister, Dmytro Kuleba, wrote on Twitter. “Russian missiles are a message to Africa: Russia wants more war, not peace.”

But if Ukrainian officials hoped that experiencing Russian bombardment firsthand might influence the African leaders’ views, there was no sign of such a shift.

Vincent Magwenya, a spokesman for Mr. Ramaphosa and member of the delegation, said that its members did not hear air-raid sirens or explosions in Kyiv. “Since our arrival, and based on where we have been, we have not witnessed any of the reported sirens or explosions,” he said. “That’s from my own experience and that of our own delegation.”

The sirens and detonations were audible across the city, but it is not clear where the delegation was at the time. Reuters reported that at one point the African officials were led into a bomb shelter beneath a hotel; in such a shelter, the noise would have been muffled or muted entirely.

Ukraine’s air defenses shot down the missiles, so the detonations took place above the city, according to the regional military administration, but falling debris injured six people and damaged several homes.

The Russian barrage on Friday included six hypersonic Kinzhal missiles — among the most sophisticated weapons in the Kremlin’s arsenal — and six Kalibr cruise missiles, all of which were destroyed before hitting their targets, Kyiv’s military administration said in a statement. The capital’s air defenses have grown very robust, but those in other parts of the country remain sparse.

The African delegation arrived in Kyiv by train from Poland. Before meeting with Mr. Zelensky, its members visited Bucha, the neighboring town where The New York Times and others have documented Russian atrocities after the invasion, and where hundreds of civilians were killed while it was under Russian occupation.

Liubov Abravitova, the Ukrainian ambassador to South Africa, said in an interview on Friday that she hoped the visit would strike an emotional chord.

“My hope is that what they’ve seen today in Bucha will always be in front of their eyes when they will be shaking hands with Putin,” she said.

In a video posted to Twitter, Mr. Magwenya said, “Africa has been severely impacted by this conflict in terms of food insecurity, the price of grain, price of fertilizer, but equally, this mission serves to seek a road to peace that will alleviate the suffering that has been experienced by people in Ukraine.”

Some analysts have questioned whether the African peace mission could realistically bear fruit, but its supporters note that among the proponents of various peace initiatives, the African delegation will be the first to meet with the leaders of both Russia and Ukraine.

“We’re here to listen, to listen to both President Zelensky and tomorrow we’ll be listening to President Putin,” Mr. Ramaphosa said. No one expects a quick resolution, he said, but African countries stand ready to mediate.

Along with Mr. Ramaphosa and Mr. Sall, the presidents of Zambia and Comoros, and representatives of Egypt, Republic of Congo and Uganda are part of the peace mission.

Neither side in the war is willing to end it on terms the other would accept. Moscow insists that Ukraine accept Russian sovereignty over the lands it has seized, demilitarize and distance itself from the NATO alliance. Kyiv insists that Russian forces leave all occupied territory.

On another diplomatic front, NATO defense ministers meeting in Brussels on Friday discussed closer cooperation with Ukraine, but the secretary-general, Jens Stoltenberg, ruled out Ukraine being offered membership when NATO heads of government meet next month in Vilnius, Lithuania.

Since 2008, NATO has had a stated goal of admitting Ukraine, a stand that has infuriated Mr. Putin. It was always considered a far-off prospect that would require Ukraine to have a more stable democracy, a more modern military and far less corruption, but since the Russian invasion, Kyiv and some of its backers in Eastern Europe have clamored for an accelerated timetable.

The United States and some other NATO nations have signaled that they are prepared to offer a long-term security commitment of weapons, training and political support to Ukraine, but are reluctant to grant membership in the near future. Admitting a nation while it is at war is widely seen as out of the question because, under NATO’s guarantee of mutual defense, it would draw the alliance directly into the conflict, which it wants to avoid.

The two-day meeting of NATO defense ministers ended on Friday without the group reaching final approval on its larger plans to bolster regional security, but Mr. Stoltenberg predicted that it would be approved in Vilnius. After Russia invaded Ukraine, the plans were revised for the first time since the end of the Cold War.

A Western defense official attributed the holdup to new Turkish objections in a longstanding dispute with other states over names of locations in the Mediterranean Sea.

U.S. Defense Secretary Lloyd J. Austin III declined to discuss any specific security assurances for Ukraine.

“Make no mistake,” he said, “we will not be drawn into Putin’s war of choice, but we will strengthen NATO’s defense and deterrence.”

Reporting was contributed by Marc Santora from Kyiv, Ukraine, Megan Specia from Lviv, Ukraine, and Lara Jakes from Brussels.