Surface-Mediated Organometallic Synthesis: High-Yield and Selective Syntheses of Neutral and Anionic Ruthenium Carbonyl Clusters by Controlled Reduction of Silica-Supported RuCl3in the Presence of Na2CO3or K2CO3

[Ru 3 (CO) 10 Cl 2 ], [Ru 3 (CO) 12 ], [H 4 Ru 4 (CO) 12 ], [H 3 Ru 4 (CO) 12 ] -, [HRu 6 (CO) 18 ] -, and [Ru 6 C(CO) 16 ] 2- have been synthesized in good or high yields by one-step or two-step (with the surface species [Ru(CO) 3 Cl 2 (HOSi⋮)] as intermediate) one-pot controlled reduction of RuCl 3 supported on silica in the presence of alkali carbonates. The selectivity of the reaction is controlled by the (i) nature and quantity of the alkali carbonate (Na 2 CO 3 or K 2 CO 3 ), (ii) manner by which the alkali carbonate is deposited on the silica surface, (iii) gas-phase composition (CO, CO + H 2, or CO + H 2 O), (iv) temperature, and (v) reaction time. The unusual selectivity can be explained by the initial formation of [Ru(CO) x (OH) 2 ] n ( x = 2, 3) which, under CO, aggregates first to [Ru 3 (CO) 12 ], key intermediate for the synthesis in situ of various ruthenium carbonyl clusters on the silica surface.