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Conversational agents are increasingly embedded in human collaborative work, yet they remain fundamentally passive and reactive: they respond to explicit user requests rather than proactively recognizing moments when a team would benefit from timely intervention as human collaborators often do. This reactive design substantially limits the use of agents as active participants in multi-user collaboration, where disagreements, ambiguous goals, forgotten constraints, underspecified plans, discussion loops, and imbalanced participation can gradually undermine group progress. To move agents from passive assistants toward active participants in multi-user collaboration, we introduce ProACT, a breakdown-aware agent framework grounded in theories of common ground, collaborative planning, and coordination work. ProACT observes the speaker-attributed conversation history, determines whether the current turn contains a collaboration breakdown requiring intervention, decides whether the agent should stay silent or speak, and, when speaking is needed, routes the case to a targeted collaboration skill. We further introduce the first multi-user collaboration benchmark for evaluating proactive agents across project planning, product design, research collaboration, logistics, education, and resource-constrained decision making. Across 3,244 turn-level examples and five LLM backbones, ProACT consistently improves collaborative appropriateness, non-interruptiveness, conciseness, and judged intervention quality over direct chat.