Pd₃ Sandwich Complexes with π-Cyclic Ligands: Theoretical Insight into Stability, Face-Capping Coordination Bond, Trans-Influence, and Backside-Ligand Effect

Triangle Pd₃ sandwich complexes with two face-capping π-cyclic ligands, [Pd₃(Cm)(Cn)L₃]²⁺ [L = acetonitrile; Cm, Cn = benzene, cycloheptatriene (CHT), cyclooctatetraene (COT), and [2.2]<i>para</i>cyclophane (PCP)], are theoretically investigated. The stability increases in the order [Pd₃(C₆H₆)₂L₃]²⁺ ∼ [Pd₃(C₆H₄Me₂^P)₂L₃]²⁺ (C₆H₄Me₂^P = <i>p</i>-xylene) < [Pd₃(COT)₂L₃]²⁺ < <b>[Pd₃(CHT)₂L₃]²⁺</b> < <b>[Pd₃(PCP)₂L₃]²⁺</b> and [Pd₃(C₆H₆)₂L₃]²⁺ ∼ [Pd₃(C₆H₆)(C₆H₄Me₂^P)L₃]²⁺ < [Pd₃(C₆H₆)(PCP)L₃]²⁺ < [Pd₃(C₆H₆)(CHT)L₃]²⁺ < <b>[Pd₃(C₆H₆)(COT)L₃]²⁺</b> < [Pd₃(CHT)(PCP)L₃]²⁺ < <b>[Pd₃(COT)(PCP)L₃]²⁺</b>, where "bold" represents an experimentally isolated complex. Based on these results, we succeeded in synthesizing a new complex [Pd₃(CHT)(PCP)L₃]²⁺. Geometrical features suggest that benzene and PCP interact with one Pd atom using one C═C double bond and with two other Pd atoms using the other C═C double bond in the bridging manner. CHT interacts with three Pd atoms using three C═C double bonds. COT interacts with three Pd atoms using three C═C double bonds in [Pd₃(COT)₂L₃]²⁺ and using π-allyl type MOs with additional participation of two C═C π bonds in [Pd₃(C₆H₆)(COT)L₃]²⁺. CHT and PCP weaken the benzene coordination bond in [Pd₃(C₆H₆)(CHT)L₃]²⁺ and [Pd₃(C₆H₆)(PCP)L₃]²⁺ like trans-influence. Unprecedentedly, COT strengthens the benzene coordination bond in [Pd₃(C₆H₆)(COT)L₃]²⁺. This "backside-ligand effect" arises from the characteristic coordination bond of the COT, which is elucidated based on the orbital interaction between the COT and Pd₃ triangle.