Surface organometallic chemistry: Facile mu(2)-carbene to mu(3)-carbyne transformation of organocobalt carbonyls on silica surface

k mu(2)-[ROC(O)C(R)]-mu(2)-(CO)Co-2-(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 [mu(3)-RC(O)OC]Co-3(CO)(9) (2a) complexes. These latter are then transformed to the corresponding (mu(3)-RC)Co-3(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.