Pyrid-2-ylidenes are trapped in solution by [Ru3(CO)12] after being formed by deprotonation of N-substituted pyridinium cations. The great basicity of these NHC ligands and the polynuclear character of the ruthenium cluster trigger room temperature orthometalation of the initial κ1-C2-pyrid-2-ylidene ligands, leading to unprecedented face-capping κ2-C2,C3-pyrid-3-yl-2-ylidene ligands.
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