The tetrahedral clusters [(C4Me4)CoRh3Cpʹ3(μ3-CO)3]+ (2; Cpʹ = C5H4Me) and [(Ph3P)AuRh3Cpʹ3(μ2-CO)3]+ (3) were synthesized by reactions of Rh3Cpʹ3(μ2-CO)3 (1b) with metalloelectrophiles [(C4Me4)Co]+ (generated from [(C4Me4)Co(C6H6)]+ under visible-light irradiation) and [(Ph3P)Au]+ (generated from (Ph3P)AuCl/Tl+). They were isolated as salts with PF6− anion, and the structures of 2PF6 and 3PF6 were determined by X-ray diffraction. The structural data gave evidence that the coordination of [(C4Me4)Co]+ occurs to the face of 1b with the CO ligands, while the [(Ph3P)Au]+ species reacts with the opposite face of 1b. The latter interaction is accompanied by elongation of the Rh–Rh bonds within the rhodium triangle by 0.1 Å. DFT calculations (at the BP86/TZP level) revealed that the selectivity of the metalloelectrophile coordination is determined by orbital control. © 2020 Elsevier B.V.