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.

四面体簇[（C ₄我₄）CoRh ₃ Cp' ₃（μ ₃ -CO）₃ ] ⁺（2 ; Cp' = C ₅ H ^ ₄ Me）中和[（PH ₃ P）AuRh ₃ Cp' ₃（μ ₂ -CO ）₃ ] ⁺（3）通过的Rh反应合成₃ Cp' ₃（μ ₂ -CO）₃（图1b）与metalloelectrophiles [（C ₄我₄）CO] ⁺（由[（C ₄ Me ₄）Co（C ₆ H ₆）] ⁺在可见光照射下产生）和[（Ph ₃ P）Au] ⁺（由（Ph ₃ P）AuCl / Tl ^+产生）。分离它们与PF盐₆ ^-阴离子，和的结构2 PF ₆和3 PF ₆通过X射线衍射确定。结构数据表明[（C ₄ Me ₄）Co] ^+的配位发生在1b的面上带有CO配体，而[（Ph ₃ P）Au] ⁺物种则与1b的相反面反应。后者的相互作用伴随着铑三角形内的Rh-Rh键延长0.1Å。DFT计算（在BP86 / TZP级别）表明，金属亲电子配位的选择性是由轨道控制确定的。