Surface organometallic chemistry: Facile μ2-carbene to μ3-carbyne transformation of organocobalt carbonyls on silica surface

μ2-[ROC(O)C(R)]-μ2-(CO)Co2(CO)5 (R = Me, iPr, tBu, Ph) bridging carbene-type dinuclear cobalt carbonyls (1) undergo a facile surface-mediated clusterification while chromatographed on silica gel, yielding [μ3-RC(O)OC]Co3(CO)9 (2a) complexes. These latter are then transformed to the corresponding (μ3-RC)Co3(CO)9 (2b) derivatives by silica-mediated decarboxylation. The X-ray diffraction structure of 2a (R = tBu) was determined and that of 2b (R = Ph) was confirmed.